Patent Application
20150311057
1. Field of the Invention
The present invention relates to an ion group irradiation device. The present invention also relates to a secondary ion mass spectrometer and method for analyzing an atom and molecule forming a sample surface.
2. Description of the Related Art
Secondary ion mass spectrometry (SIMS) is an analysis method involving identifying an atom species or molecule species forming a sample surface by irradiating a sample with a primary ion beam and measuring a mass-to-charge ratio of secondary ions emitted from the sample surface. The SIMS has features of, for example, having high sensitivity, being able to comprehensively analyze multiple kinds of molecules, and being able to analyze a sample surface two-dimensionally with a high spatial resolution. Owing to those features, in recent years, a method involving identifying multiple kinds of molecules forming a biological tissue and visualizing a fine two-dimensional distribution state of the molecules through use of the SIMS has been drawing attention.
In the SIMS, secondary ions are emitted through a sputtering phenomenon caused by collision between primary ions and sample molecules. The secondary ions include a great number of ions such as those which are ionized without a molecular structure of sample molecules being decomposed (hereinafter referred to as “precursor ions”) and those which are ionized with a molecular structure being decomposed by sputtering (hereinafter referred to as “fragment ions”). Therefore, a secondary ion mass spectrum to be obtained includes a precursor ion peak and a fragment ion peak, and a sample molecular species may not be identified in some cases. In particular, in the case where a great number of molecule species are mixed as in a biological tissue, it is very difficult to identify the sample molecule species.
There has been proposed a procedure for extracting a peak derived from a precursor ion from a secondary ion mass spectrum by irradiating a sample with multiple species of ions. Japanese Patent Translation Publication No. 2011-501367 discloses a method using two kinds of liquid metal ions (e.g., bismuth and manganese) as primary ions. In this method, a spectrum of a precursor ion is extracted by subjecting a secondary ion mass spectrum obtained through the irradiation of each kind of primary ions to difference analysis.
On the other hand, a primary ion irradiation device has also been developed so as to suppress the decomposition of a sample molecule. Hitherto, it has been considered that metal cluster ions formed of a liquid metal such as gold or bismuth or polyatomic ions mainly containing fullerene are used as primary ions. Further, in recent years, gas cluster ions have been drawing attention as primary ion sources. The gas cluster ions have a large cluster size, and hence kinetic energy per atom becomes small, with the result that decomposition of sample molecules is suppressed. Japanese Patent Application Laid-Open No. 2011-29043 discloses an apparatus for controlling the kinetic energy per atom of gas cluster ions to 20 eV or less.
The related-art SIMS apparatus has a problem in that it is difficult to distinguish a peak of precursor ions from a peak of fragment ions in a secondary ion mass spectrum to be obtained.
When an ion source disclosed in Japanese Patent Translation Publication No. 2011-501367 is used, available ion species are limited to a very small number, and fragment ions are increased in intensity irrespective of the used ion species. Therefore, there is a problem in that sufficient peak distinction from precursor ions cannot be performed.
When the apparatus disclosed in Japanese Patent Application Laid-Open No. 2011-29043 is used, fragment ions are relatively reduced in intensity, but are not completely eliminated. Therefore, there still remains a problem in that it is difficult to distinguish precursor ions from fragment ions.
Meanwhile, in another case, when a sample is irradiated with two or more kinds of primary ions having different masses, and two or more kinds of secondary ion mass spectra thus obtained are compared to each other, the sample molecular species can be easily identified.
On the other hand, a method of irradiating a sample with two or more kinds of primary ions takes long measurement time, and hence there is another problem in that sample molecules cannot be identified with satisfactory throughput.
Various procedures for shortening the measurement time have been devised. Japanese Patent No. 3358065 discloses a technology of collectively irradiating a sample with an ion group obtained by dividing one ion group into n sub-ion groups having fine time intervals as primary ions. A reflecting the fine time intervals of the primary ions is obtained, and intensities of n peaks corresponding to a specified secondary ion species are accumulated. In general, according to the SIMS, in order to ensure a mass resolution of secondary ions, one ion group having a shorter time width is generated from one ion group, and in this case, the number of ions included in the ion group decreases, with the result that measurement takes time in order to obtain a sufficient secondary ion intensity. In Japanese Patent No. 3358065, a sample can be irradiated with primary ions without any loss of ions, and hence the measurement time can be shortened.
A technology of identifying a sample molecular species with satisfactory throughput by enhancing detection sensitivity of precursor ions by irradiation with primary ions for suppressing decomposition of sample molecules has also been developed. As mentioned above, Japanese Patent Application Laid-Open No. 2011-29043 discloses an apparatus for controlling the kinetic energy per atom of gas cluster ions to 20 eV or less.
As also mentioned above, the related-art SIMS apparatus has a problem in that it is difficult to distinguish precursor ions from fragment ions in a secondary ion mass spectrum to be obtained. When two or more kinds of secondary ion mass spectra are obtained by irradiation with two or more kinds of primary ions having different masses so as to solve the above-mentioned problem, there arises a problem in that measurement time becomes long.
According to the method disclosed in Japanese Patent No. 3358065, a spectrum in which n secondary ion mass spectra of the single kind are superimposed on each other is obtained instead of two or more kinds of secondary ion mass spectra. Therefore, measurement time can be shortened, but an ability to distinguish a precursor ion peak from a fragment ion peak is not improved.
In addition, as mentioned above, when the apparatus disclosed in Japanese Patent Application Laid-Open No. 2011-29043 is used, fragment ions are relatively reduced in intensity, but are not completely eliminated. Therefore, there still remains a problem in that it is difficult to distinguish precursor ions from fragment ions.
According to one embodiment of the present invention, there is provided an ion group irradiation device, including: an ion source for generating ions; an ion group selecting unit configured to select, from the ions released from the ion source, two or more ion groups formed of ions having different average masses; and a primary ion irradiation unit configured to irradiate a sample with the two or more ion groups selected by the ion group selecting unit, in which an atom species and/or a molecule species of the ions forming the two or more ion groups is common between ion groups.
The ion group irradiation device of one embodiment of the present invention can distinguish a peak of a precursor ion from a peak of a fragment ion based on a difference between multiple kinds of secondary ion mass spectra, which facilitates the identification of a sample molecule.
According to another embodiment of the present invention, there is provided an ion group irradiation device for irradiating a sample with an ion group, including: an ion source for generating ions; an ion group selecting unit configured to select, from the ions released from the ion source, two or more ion groups formed of ions having different average masses; and a primary ion irradiation unit configured to irradiate the sample with the two or more ion groups selected by the ion group selecting unit. The ion group selecting unit selects one or more ion groups and further selects the two or more ion groups from each of the selected one or more ion groups.
In the ion group irradiation device of the present invention, two or more kinds of secondary ion mass spectra can be obtained in short measurement time, and hence distinction of peaks between precursor ions and fragment ions and identification of a sample molecular species can be performed with satisfactory throughput.
Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
Preferred embodiments of the present invention will now be described in detail in accordance with the accompanying drawings.
The application of an ion irradiation device of the present invention is not particularly limited and may be used as a part of a secondary ion mass spectrometer or as a surface treatment device or a surface modifying device. In the following description, embodiments in which the ion irradiation device of the present invention is used as a part of the secondary ion mass spectrometer are described in detail. Note that, the following descriptions of each embodiment and illustrations of the drawings are merely exemplifications of the present invention, and the present invention is not limited to those descriptions and illustrations even in the case where nothing is particularly referred to. Further, the case of carrying out the present invention by combining multiple examples within a range not causing any contradiction also falls in the scope of the present invention.
There is provided an ion group irradiation device for irradiating a sample with an ion group, including: an ion source for generating ions; an ion group selecting unit configured to select, from the ions released from the ion source, two or more ion groups formed of ions having different average masses; and a primary ion irradiation unit configured to irradiate the sample with the two or more ion groups selected by the ion group selecting unit. The ion group selecting unit selects one or more ion groups and further selects the two or more ion groups from each of the selected one or more ion groups.
A first embodiment of the present invention is described with reference to
An ion group selecting unit of the present invention selects an ion group from ions released from an ion source and further selects two or more ion groups from the one selected ion group. In the specification of the present application, description is made defining an ion group selected from ions released from the ion source to be a first ion group and defining two or more ion groups selected from the one first ion group to be second ion groups. In
An ion group irradiation unit irradiates a sample with the second ion groups 2, 3, and 4 including two or more selected ion groups. In the specification of the present application, the second ion groups with which the sample is to be irradiated are sometimes referred to as primary ions. The ion source refers to a unit configured to generate and release ions from an ion material, that is, a unit configured to generate ions. As illustrated in
The first and second ion groups are respectively formed of two or more ions. The two or more ions respectively have a specified mass. The kind of an ion is determined based on an atom or an atom group, a mass, and a valence of an ion. When the atom or the atom group of an ion varies, the mass of the ion varies. Further, the kind of an ion group is determined based on the kind of ions forming the ion group. Thus, when the kind of ions forming an ion group varies, at least the kind of the ion group varies, and at least the average mass of ions forming the ion group varies.
The first ion group 1 is obtained by selecting a part of ions released from the ion source, in which various kinds of ions are mixed. In the example of
The second ion groups 2, 3, and 4 are obtained by selecting specified ions as target ions from the first ion group in which various kinds of ions are mixed. In the example of
Note that, an ion group being formed of one kind of ions refers to that two or more ions are identical in terms of an atom, an atom group, a mass, and a valence. Note that, in the case where ions are cluster ions (described later), when the ions are selected as an ion group, a mass distribution has a width to some degree; therefore, one group present in a predetermined mass distribution may be defined as one kind of ions.
In the case where the mass distribution of cluster ions in the above-mentioned one group follows a normal distribution N (μ, σ2) (where μ: mean, σ2: variance), one kind of cluster ions includes ions shifted from μ by preferably ±3σ, more preferably ±σ. Also in the case where the molecular weight of the cluster ions follows a distribution other than the normal distribution, the cluster ions are defined accordingly.
Even in the case where the mass distribution of the cluster ions in the above-mentioned one group does not have a complete symmetric form, if there is one peak and a half-value width is sufficiently small, those ions can be defined as one kind of cluster ions.
Further, an ion group being formed of one kind of ions includes the case where an ion group includes a trace amount of ions other than the one kind of ions to such a degree as not to interfere analysis.
For example, the ion group 2 is formed of the ions 13, but may include a trace amount of the ions 14 or the other ions to such a degree as not to interfere analysis of the mass spectrometer of the present invention. When the proportion of ions mixed with one kind of ions is high, the time width of an ion group is likely to be enlarged before the ion group reaches a sample, and the time width of secondary ions obtained from the sample becomes large, with the result that mass resolution is degraded. The degree to which measurement is not interfered refers to a degree to which the above-mentioned problem is not caused, and the proportion is preferably 10% or less, more preferably 1% or less.
The average mass of an ion group is determined by various conditions such as the kind and supply pressure of an ion material to be used, the configurations of various components in an ion group irradiation device, and selection conditions such as the applied voltage and time for selecting the first and second ion groups. For example, in the case of selecting the first ion group under the same selection conditions in the same ion material and supply pressure and the same ion group irradiation device, an ion group formed of ions having different average masses can be selected by changing selection conditions of the second ion group.
As the average mass in the present invention, an average mass in a mass spectrum of an ion group may be used or a mass obtained by calculating an average mass through use of various conditions such as the kind of the ion group, the configuration of the ion group irradiation device, and the selection conditions of the first and second ion groups. The mass spectrum of an ion group can be obtained by mass spectrometry of an ion group, and may be measured in the apparatus of the present invention or may be measured in another apparatus in advance. In the case of measuring a mass spectrum in the apparatus of the present invention, for example, a micro-channel plate (MCP) is set in the vicinity of a sample, and the sample is irradiated with the second ion group selected by changing the selection conditions of the second ion group. Regarding two or more second ion groups, an average mass of ions forming each ion group is obtained from two or more peaks of a mass spectrum measured by the MCP.
Note that, even in the case of one kind of ions, two or more ions actually generated from the ion source have existing positions and kinetic energies varying for each ion in a space in the vicinity of the ion source. Therefore, the conditions such as time and an applied voltage required for selecting two or more ions of one kind as one ion group and detecting the one ion group with a detector vary for each ion. Due to this variation, a mass spectrum obtained by actual measurement has a continuous spectrum having a width even in an ion group formed of ions having the same mass. In addition, the half-value width of a mass spectrum becomes larger as the number of kinds of ions included in an ion group is larger.
In the present invention, two or more second ion groups include two or more ion groups having different average masses. When the kind of ions forming an ion group varies, the average mass of the ions forming the ion group varies. As illustrated in
Further, in the present invention, the time interval between first ion groups to be selected is not particularly limited as long as the time interval 6 is larger than any one of the time difference 7 from the second ion group, the sum of the time differences 7 and 11, and the sum of the time differences 7 and 12, but preferably 10 μsec to 100 msec. Further, the time width 5 of the first ion group is not particularly limited, but is preferably 0.1 nsec to 50 μsec. Further, all of the time difference 7 between the first ion group and two or more second ion groups, the sum of the time differences 7 and 11, and the sum of the time differences 7 and 12 are not particularly limited, but preferably 0.1 μsec to 10 msec. Further, the time widths 8, 9, and 10 of the second ion groups are not particularly limited, but preferably 0.1 nsec to 50 μsec.
A sample is irradiated with the second ion groups selected as described with a time difference by the ion group irradiation unit. Note that, in the case where samples to be irradiated with the second ion groups are not the same or different regions of the same sample are irradiated with the second ion groups, the irradiation may be performed simultaneously. This time difference may be the same as or different from a time difference (11, 12 in
The same surface region of the same sample may be irradiated with two or more ion groups of the present invention, multiple surface regions of the same sample may be irradiated with the two or more ion groups of the present invention, or the irradiation of the two or more ion groups may be varied for each sample and region.
When the same surface region of the same sample is irradiated with the two or more ion groups of the present invention, a molecule species can be identified in an irradiation region with satisfactory throughput by secondary ion mass spectrometry. In addition, in the case where secondary ion mass spectrometry in a depth direction is intended, analysis can be performed while a sputtering rate with respect to a surface is being changed easily at a high speed. Further, in the case where surface treatment or surface modification is intended, the surface treatment or the surface modification can be performed with satisfactory throughput while an etching rate, surface roughness, and a coating film thickness are being changed easily.
When multiple different surface regions of the same sample are irradiated, an ion group suitable for target molecules can be selected for each region, and secondary ion mass spectrometry can be performed with satisfactory throughput. In addition, previous study for selecting an ion group suitable for a sample and target molecules can be performed with satisfactory throughput. Further, in the case where surface treatment or surface modification is intended, a surface having an etching depth, surface roughness, and a coating film thickness varying for each of multiple surface regions can be obtained with satisfactory throughput.
The ions in the present invention refer to charged atoms or atom group and include all ions. As preferred examples of the ions, there may be given various cluster ions. The cluster refers to an object in which two or more atoms or molecules are bound by an interaction such as a Van der Waals' force, an electrostatic interaction, a hydrogen bond, a metallic bond, or a covalent bond, and the cluster ion refers to a charged cluster. Further, the cluster ion may be formed of one kind of atom or molecule, or two or more kinds of atoms or molecules. Note that, an ion formed of one atom or molecule is called a monomer ion, which is discriminated from the cluster ion. For example, an ion formed of one water molecule is not a cluster ion but a monomer ion. Note that, only in the case of a fullerene molecule formed of 60 carbon atoms, one fullerene molecule may be exceptionally regarded as a cluster ion.
In the case where the ion is a cluster ion, as a preferred example of the first ion group in the present invention, there may be given the following. Specifically, the first ion group is formed of two or more cluster ions of two or more kinds, and the two or more cluster ions of two or more kinds refer to those which are selected from the same ion source, that is, those in which atoms or molecules forming each unit of respective clusters are the same and only the number of units forming the cluster is different (for example, cluster ions formed of X gold atoms and cluster ions formed of Y gold atoms).
Preferred examples of the cluster ions in the present invention include cluster ions formed of gold, bismuth, xenon, argon, and water, and ions of fullerene which is a cluster formed of carbon.
Examples of the cluster ions of gold include cluster ions in which 2 to 1,000 gold atoms are bound through a metallic bond and ionized. Examples of the cluster ions of bismuth include cluster ions in which 2 to 1,000 bismuth atoms are bound through a metallic bond and ionized. Examples of the cluster ions of argon include cluster ions in which 2 to 100,000 argon atoms are aggregated by the Van der Waals' force and ionized. Examples of the cluster ions of water include cluster ions in which 2 to 100,000 water molecules are bound through a hydrogen bond and ionized. Examples of the cluster ions of carbon include fullerene in which 60 carbon atoms are bound through a covalent bond and fullerene ions in which 2 to 1,000 fullerenes are further aggregated by the Van der Waals' force and ionized.
Further, as preferred examples of ions other than the cluster ions in the present invention, there may be given monomer ions. Specific examples thereof include monatomic ions each formed of one atom such as gold, bismuth, argon, and xenon; and monomolecular ions each formed of one molecule such as water.
Note that, in the specification of the present application, in the case where the ions are cluster ions, one cluster ion is considered as one ion irrespective of the form of a bond in a cluster, and the mass of ions refers to a mass obtained by subtracting a mass of lost electrons from the total mass of atoms forming the ion or a mass obtained by adding a mass of added electrons to the total mass of the atoms forming the ion. Further, in the specification, the term “particle” may be used as a concept including an atom, a molecule, and a cluster.
Further, that cluster ions have the same ion species refers to that elements forming a cluster, and the number, bond form, and valence of the elements are the same.
In the present invention, ions are generated from an ion material. The kind and state of the ion material are not particularly limited, and may be neutral particles or an aggregate of charged particles. The particle may be a single particle or a mixture of multiple particles, or may include multiple atoms or molecules. The ion material may be in any state of a gas, a liquid, or a solid at normal temperature and normal pressure, in a mixed state of a gas and a liquid, or in a state in which a solid is dissolved in a gas or a liquid.
For example, as a material for a cluster ion of gold, there may be given neutral gold. When an emitter obtained by applying a tungsten needle with neutral gold is heated, and an electrostatic field is applied between an emitter tip end and an extraction electrode, gold can be ionized by an electric field radiation and extracted into a vacuum, with the result that a gold cluster ion can be generated. As a material for a cluster ion of bismuth, there may be given neutral bismuth. When an emitter obtained by applying neutral bismuth to a tungsten needle is heated, and an electrostatic field is applied between an emitter tip end and an extraction electrode, bismuth can be ionized by an electric field radiation and extracted into a vacuum, with the result that a bismuth cluster ion can be generated. As a material for a cluster ion of xenon, there may be given xenon gas. Xenon gas is in a state of a gas at normal temperature and normal pressure. When xenon gas is jetted into a vacuum, neutral xenon gas clusters are generated by adiabatic expansion. When xenon gas clusters are irradiated with an electron beam, xenon gas cluster ions are generated. As a material for a cluster ion of argon, there may be given argon gas. Argon gas is in a state of a gas at normal temperature and normal pressure. When argon gas is jetted into a vacuum, neutral argon gas clusters are generated by adiabatic expansion. When argon gas clusters are irradiated with an electron beam, argon gas cluster ions are generated. As a material for a cluster ion of water, there may be given a neutral water molecule. Water is in a state of a liquid at normal temperature and normal pressure. When cluster ions of water are jetted into a vacuum in a state of liquid water or gasified vapor, neutral water clusters are generated by adiabatic expansion. When the water clusters are irradiated with an electron beam, water cluster ions are generated. As a material for ions of fullerene, there may be given fullerene. When neutral fullerene gas generated by gasifying fullerene is irradiated with an electron beam, fullerene ions can be generated.
An ion species included in an ion group with which a sample is irradiated may be appropriately selected depending on the kind of sample molecules to be detected. For example, the detection sensitivity can be enhanced in some cases by adding an ion to a target molecule intentionally. Examples of the ion to be added include a hydrogen ion, a sodium ion, a potassium ion, an ammonia ion, a silver ion, a gold ion, and a chlorine ion.
An ion species included in an ion group with which a sample is irradiated can be selected by selecting an ion material to be used or by the ion group selecting unit. For example, in the case where it is intended to add a hydrogen ion, an ion species containing a great amount of hydrogen can be easily generated by incorporating any one of water, an acid, and an alcohol into an ion material. In addition, in the case where it is intended to add a sodium ion, a potassium ion, an ammonia ion, a silver ion, a gold ion, or a chlorine ion, an organic salt or inorganic salt containing sodium, potassium, silver, gold, or chlorine may be incorporated into the ion material. A typical substance of the sodium salt is, for example, sodium formate, sodium acetate, sodium trifluoroacetate, sodium hydrogen carbonate, sodium chloride, or sodium iodide. Even when the organic salt or inorganic salt itself is a solid, the salt may be easily used as the ion material by being added to a liquid such as water.
Further, the time width of the ion group is not particularly limited, but is preferred to be 0.1 nsec to 50 μsec.
In another embodiment of the present invention, there is provided a secondary ion mass spectrometer including an ion source for generating ions, an ion group selecting unit configured to select, from ions released from the ion source, two or more ion groups formed of ions having different average masses, and a primary ion irradiation unit configured to irradiate a sample with the two or more ion groups selected by the ion group selecting unit, in which an atom species and/or a molecule species of the ions forming the two or more ion groups is common between the two or more ion groups.
This embodiment is described with reference to
Two or more ion groups (137, 138, 139, 140, 141) of the present invention are selected by the ion group selecting unit from ions released from the ion source, and a sample is irradiated with the two or more ion groups by the ion group irradiation unit. The ion source refers to a unit configured to generate and release ions from an ion material. As illustrated in
The ion group is formed of two or more ions. The two or more ions respectively have a specified mass. The kind of an ion is determined based on an atom or an atom group, a mass, and a valence of an ion. When the atom or the atom group of an ion varies, the mass of the ion varies. Further, the kind of an ion group is determined based on the kind of ions forming the ion group. Thus, when the kind of ions forming an ion group varies, at least the kind of the ion group varies, and at least the average mass of ions forming the ion group varies. The ion groups 137, 138, 139, 140, and 141 are selected from an aggregate of ions which is released from the ion source and in which various kinds of ions are mixed, with ions having a specified mass being target ions. In the example of
Note that, an ion group being formed of one kind of ions refers to that two or more ions are identical in terms of a mass. Note that, in the case where ions are cluster ions (described later), when the ions are selected as an ion group, a mass distribution has a width to some degree; therefore, one group present in a predetermined mass distribution may be defined as one kind of ions.
In the case where the mass distribution of cluster ions in the above-mentioned one group follows a normal distribution N (μ, σ2) (where μ: mean, σ2: variance), one kind of cluster ions includes ions shifted from μ by preferably ±3σ, more preferably ±σ. Also in the case where the molecular weight of the cluster ions follows a distribution other than the normal distribution, the cluster ions are defined accordingly.
Even in the case where the mass distribution of the cluster ions in the above-mentioned one group does not have a complete symmetric form, if there is one peak and a half-value width is sufficiently small, those ions can be defined as one kind of cluster ions.
Further, an ion group being formed of one kind of ions includes the case where an ion group includes a trace amount of ions other than the one kind of ions to such a degree as not to interfere analysis.
For example, the ion group 137 is formed of the ions 144, but may include, as in the ion group 141, a trace amount of the ions 145 or the other ions to such a degree as not to interfere analysis of the mass spectrometer of the present invention. When the proportion of ions mixed with one kind of ions is high, the time width of an ion group is likely to be enlarged before the ion group reaches a sample, and the time width of secondary ions obtained from the sample becomes large, with the result that mass resolution is degraded. The degree to which measurement is not interfered refers to a degree to which the above-mentioned problem is not caused, and the proportion is preferably 10% or less, more preferably 1% or less.
The two or more ion groups of the present invention are formed of ions including an atom species or molecule species which is common between the ion groups. As illustrated in
The ions forming the two or more ion groups of the present invention have different average masses between the ion groups.
The ions forming the two or more ion groups of the present invention include an atom species or molecule species common between the ion groups and have different average masses. That is, as illustrated in
The average mass in a mass spectrum can be determined from the mass of ions included in the ion groups and the signal intensity (number) of ions of each mass. The theoretical value of the mass of the ions is a discrete value based on an element composition and a valence. Note that, in actual, two or more ions generated from the ion source have existence positions and kinetic energies varied for each ion in a space in the vicinity of the ion source, even if the two or more ions have the same mass. Therefore, the conditions such as time and an applied voltage required for selecting two or more ions having the same mass as one ion group and detecting it with a detector vary for each ion. Due to this variation, a mass spectrum obtained by actual measurement has a continuous spectrum having a width even in an ion group formed of ions having the same mass. In addition, the half-value width of a mass spectrum becomes larger as the number of kinds of ions included in the ion group is larger. For example, in
According to one embodiment of the present invention, there is provided an ion group irradiation device for irradiating a sample with an ion group, including: an ion source for generating ions; an ion group selecting unit configured to select, from the ions released from the ion source, two or more ion groups formed of ions having different average masses; and a primary ion irradiation unit configured to irradiate the sample with the two or more ion groups, in which an atom species or a molecule species of the ions forming the two or more ion groups is common between ion groups.
In the ion group irradiation device, the ion group selecting unit includes a first chopper positioned on the ion source side, a second chopper, and an ion separator disposed between the first chopper and the second chopper. The first chopper and the second chopper each perform a chopping operation of selecting an ion group by passing and blocking the ions in a traveling direction through opening and closing. The second chopper performs one chopping operation in coordination with one chopping operation by the first chopper. In a specified cycle in which the chopping operation by the first chopper and the chopping operation by the second chopper are repeated multiple times, there are multiple differences between an opening time of the first chopper and an opening time of the second chopper.
Although the ion separator is not particularly limited, the ion separator is preferred to be a time-of-flight mass separator.
The ion group irradiation device may include an intermittent valve for supplying an ion material.
Although the two or more ion groups are not particularly limited, it is preferred that the same sample be irradiated with the two or more ion groups. It is also preferred that the same region be irradiated with the two or more ion groups at different times. It is also preferred that the sample be irradiated with the two or more ion groups in the order from an ion group formed of ions having a larger average mass in a certain period of time.
The sample may be irradiated coaxially with the two or more ion groups. Although the number of irradiations of the two or more ion groups is not particularly limited, the number of irradiations may be determined based on an ion current value of the ions included in the ion groups with which the sample is irradiated. Further, the two or more ion groups may include three or more ion groups in which ions forming the ion groups have different average masses and one of an atom species or a molecule species of the ions forming the ion groups is common between the ion groups. At least one of the two or more ion groups may be formed of cluster ions.
Although the ion material is not particularly limited, the ion material may contain a substance that is a gas or a liquid at normal temperature and normal pressure.
At least one of the two or more ion groups may include at least one kind of molecules of water, an acid, and an alcohol. At least one of the two or more ion groups may include rare gas molecules. The atom species or molecule species of the ions forming the two or more ion groups may be the same between the ion groups.
Although there is no limit to a configuration ratio of the atom species or molecule species of the ions forming the two or more ion groups, the configuration ratio is preferred to be equal between the ion groups.
A method of generating ions from the ion material may include electron impact ionization.
At least one of the first chopper or the second chopper may include a chopper formed of a combination of a deflection electrode and an aperture.
Further, according to one embodiment of the present invention, there is provided a secondary ion mass spectrometer, including: the ion group irradiation device described above; and a mass spectrometer for measuring a mass of a secondary ion generated from a sample irradiated with an ion group by the ion group irradiation device. Although the secondary ion mass spectrometer is not particularly limited, the secondary ion mass spectrometer may be a time-of-flight mass spectrometer.
The secondary ion mass spectrometer may include a detector having a two-dimensional ion detection function of detecting the secondary ion generated from a sample surface while keeping a positional relationship at a secondary ion generation position.
The secondary ion mass spectrometer may further include an analysis device for performing comparison analysis with respect to two or more secondary ion mass spectra or two or more mass distribution images.
Further, according to one embodiment of the present invention, there is provided a secondary ion mass spectrometry method, including: comparing secondary ion mass spectra for each ion group for irradiation; and obtaining a mass spectrum or a mass distribution image based on a difference between the secondary ion mass spectra, through use of the secondary ion mass spectrometer described above.
Further, according to one embodiment of the present invention, there is provided a secondary ion mass spectrometer for irradiating a sample with an ion group, including: an ion source for generating ions; an ion group selecting unit configured to select two or more ion groups from the ions released from the ion source; and a primary ion irradiation unit configured to irradiate the sample with the two or more ion groups. The ion group selecting unit includes a first chopper positioned on the ion source side, a second chopper, and an ion separator disposed between the first chopper and the second chopper. The first chopper and the second chopper each perform a chopping operation of selecting an ion group by passing and blocking the ions in a traveling direction through opening and closing. The second chopper performs one chopping operation in coordination with one chopping operation by the first chopper. In a specified cycle in which the chopping operation by the first chopper and the chopping operation by the second chopper are repeated multiple times, there are multiple differences between an opening time of the first chopper and an opening time of the second chopper.
Further, according to one embodiment of the present invention, there is provided a secondary ion mass spectrometer for irradiating a sample with an ion group, including: an ion source for generating ions; an ion group selecting unit configured to select two or more ion groups from the ions released from the ion source; and a primary ion irradiation unit configured to irradiate the sample with the two or more ion groups. The ion source includes an intermittent valve. The ion group selecting unit includes a first chopper positioned on the ion source side, a second chopper, and an ion separator disposed between the first chopper and the second chopper. The intermittent valve performs a jetting operation of intermittently jetting an ion material. The first chopper and the second chopper each perform a chopping operation of selecting an ion group by passing and blocking the ions in a traveling direction through opening and closing. The secondary ion mass spectrometer is operated in: a first operation mode in which at least one of the first chopper or the second chopper performs the chopping operation multiple times in coordination with one jetting operation by the intermittent valve; a second operation mode in which the second chopper performs one chopping operation in coordination with one chopping operation by the first chopper, and in a specified cycle in which the chopping operation by the first chopper and the chopping operation by the second chopper are repeated multiple times, there are multiple differences between an opening time of the first chopper and an opening time of the second chopper; and a third operation mode in which the second chopper performs the chopping operation multiple times in coordination with one chopping operation by the first chopper. The secondary ion mass spectrometer is operated in a combination of at least two of the first operation mode, the second operation mode, and the third operation mode.
The above embodiments are further described with reference to
Secondary ions generated through irradiation are analyzed by the mass spectrometer 20 and analyzed by the analysis device 21 each time, and secondary ion mass spectra 33 and 34 different from each other are obtained from the output device 22. The obtained secondary ion mass spectra 33 and 34 may be subjected to difference analysis between the spectra and output. Further, a mass distribution image may be analyzed and output. One or two or more mass spectrometers 20 may be used. It is preferred that one mass spectrometer 20 be used from the viewpoint of an apparatus size and an operation cost.
The primary ion irradiation device 19 of
In another embodiment, a first ion group is selected from ions released from the ion source 27 by the ion group selecting unit 28, and further two or more second ion groups are selected from one first ion group. The selected ion groups are accelerated to several to several 10 KeV by a potential difference from the ion group selecting unit 28 or the ion group irradiation unit 29 to a sample surface, and a specified region on the sample surface is irradiated with the ion groups. Note that, the ion group irradiation unit 29 may be a part of the ion group selecting unit 28, and in this case, the ion group irradiation unit 29 may not be provided separately.
Further, the ion group irradiation unit 29 may include a converging electrode for converging an irradiation diameter of an ion group, a re-acceleration electrode for re-accelerating ions or an ion group, and a deflection electrode for deflecting ions or an ion group. One or two or more primary ion irradiation units may be used. It is preferred that one primary ion irradiation unit be used from the viewpoint of an apparatus size and an operation cost. However, when different regions of the same sample or different samples are irradiated with two or more ion groups simultaneously, two or more primary ion irradiation units 5 may be used. Further, one or two or more ion sources 27, ion group selecting units 28, and ion group irradiation units 29 may be included in one primary ion irradiation unit.
The ion source 27 includes at least an ion material and an ion material supply unit. Further, in the case where the ion material is uncharged neutral particles, that is, neutral atoms or molecules, a neutral cluster, or the like, the ion source 27 includes an ionization unit. Further, as needed, a skimmer for removing excessively large neutral particles or a buffer container for differential evacuation may be provided between the ion material supply unit and the ionization unit.
The ion material refers to a substance to be a material for ions serving as primary ions with which a sample is irradiated. The kind and state of the ion material are not particularly limited, and the ion material is an aggregate of neutral or charged particles. The particles may be formed of one kind of atom or molecule, or may be formed of a mixture of multiple kinds of atoms or molecules. The ion material may be in a state of a gas, a liquid, or a solid at normal temperature and normal pressure. The ion material may also be in a mixed state of a gas and a liquid or in a state in which a solid is dissolved in a gas or a liquid. Preferred examples of the gas include: rare gases such as argon and xenon; and oxygen. Preferred examples of the liquid include water, an acid, an alcohol, and an alkali. Preferred examples of the solid include metals such as gold and bismuth, and fullerene.
An ion species included in an ion group with which a sample is irradiated may be appropriately selected depending on the kind of sample molecules to be detected. For example, the detection sensitivity can be enhanced in some cases by adding an ion to a target molecule intentionally. Examples of the ion to be added include a hydrogen ion, a sodium ion, a potassium ion, an ammonia ion, a silver ion, a gold ion, and a chlorine ion.
An ion species included in an ion group with which a sample is irradiated can be selected by selecting an ion material to be used or by the ion group selecting unit. For example, in the case where it is intended to add a hydrogen ion, an ion species containing a great amount of hydrogen can be easily generated by incorporating any one of water, an acid, and an alcohol into an ion material. In addition, in the case where it is intended to add a sodium ion, a potassium ion, an ammonia ion, a silver ion, a gold ion, or a chlorine ion, an organic salt or inorganic salt containing sodium, potassium, silver, gold, or chlorine may be incorporated into the ion material. A typical substance of the sodium salt is, for example, sodium formate, sodium acetate, sodium trifluoroacetate, sodium hydrogen carbonate, sodium chloride, or sodium iodide. Even when the organic salt or inorganic salt itself is a solid, the salt may be easily used as the ion material by being added to a liquid such as water.
The structure of the ion material supply unit is not limited, and for example, the ion material supply unit can include a container for holding an ion material, a nozzle or an emitter for supplying an ion material, and a heating and pressurizing mechanism. The ion material supply unit may supply an ion material intermittently or continuously. It is preferred that an ion material be supplied intermittently, for example, through use of an intermittent valve from the viewpoint of maintaining a vacuum state of the device. The ion material supply unit may have a function of generating ions so as to be grouped for each mass. For example, the ion material supply unit may include a temperature regulator for separating ions based on a difference in boiling point or melting point, and an aerodynamic particle diameter distribution measurement device for separating ions based on a difference in particle diameter.
An ionization method, such as one used by the ionization unit, is not particularly limited, and examples thereof include electron impact ionization, chemical ionization, photoionization, surface ionization, a field-emission method, plasma ionization, penning ionization, and an electrospray ionization. Note that, in the case where an electrospray ionization is used in the ionization unit, it is only required to apply a high voltage of about several kV to a nozzle tip end of the ion material supply unit. Further, ionization may be performed continuously or intermittently in the ionization unit. For example, in ionization of a gas such as a rare gas such as argon or xenon, or oxygen, monatomic ions and cluster ions are obtained by performing electron impact ionization with respect to neutral cluster particles generated by jetting the rare gas to the vacuum through a nozzle. Further, in ionization of a liquid such as water, an acid, an alcohol, or an alkali, monomolecular ions and cluster ions are obtained by heating the liquid with the ion material supply unit to obtain a gas and performing electron impact ionization with respect to the gas in the same way as in the rare gas or the like. Further, in the other methods, water, an acid, or an alcohol is allowed to flow as a liquid through a nozzle in a vacuum, and a high voltage of about several kV is applied to a tip end of the nozzle, whereby the liquid can be ionized by an electrospray method. Further, in ionization of a metal such as gold or bismuth, monatomic ions and cluster ions are obtained by a field-emission method by heating a metal applied to a tungsten emitter in a vacuum and applying an electrostatic field between an extraction electrode and a tip end of the emitter. In ionization of fullerene, monomolecular ions and cluster ions are obtained by heating fullerene with the ion material supply unit to obtain a gas and performing electron impact ionization with respect to the gas in the same way as in the rare gas or the like. Note that, ionization may be performed continuously or intermittently in the ionization method.
The ion group selecting unit includes a first ion group selecting unit configured to select a first ion group from ions generated from an ion source, and a second ion group selecting unit configured to select two or more second ion groups from one first ion group. The first and second ion group selecting units may have a part in common or may be independent from each other. An ion group with which a sample is irradiated can be generated with more satisfactory efficiency by selecting two or more second ion groups from one first ion group than selecting one second ion group from one first ion group. Therefore, measurement time can be shortened even in the case where a sample is irradiated with two or more ion groups having different average masses of ions forming the ion groups.
As the ion group selecting unit, various ion separators and choppers, or a combination thereof can be used. The ion separator refers to a unit configured to separate an aggregate formed of multiple kinds of ions in a gaseous phase based on properties (mass, charge number, three-dimensional shape, etc.) of ions. The ion separator is not particularly limited, and a time-of-flight mass separator, a quadrupole mass separator, an ion-trap mass separator, a magnetic mass separator, an ExB filter, an ion mobility separator, or the like is preferably used. The chopper is a unit configured to intermittently pass ions by repeating opening and closing. The ions are divided in the traveling direction with the chopper, and one or more ion groups are selected. The chopping operation refers to an operation of selecting one or more ion groups by passing and blocking ions in the traveling direction by opening and closing of the chopper. The chopper blocks ions in the traveling direction in a closed state and passes ions in the traveling direction in an opened state. The operation in which the chopper changes from a closed state to a closed state again after undergoing an opened state for a predetermined period of time is counted as one chopping operation. The configuration of the chopper is not particularly limited, and a combination of a deflection electrode and an aperture, a mesh-shaped retarding electrode, a circular flat plate with an aperture which rotates at a high speed, or the like is preferably used. In the present invention, a combination of a deflection electrode and an aperture can be more preferably used from the viewpoint of operation timing controllability and ion convergence.
The drive method for an opening and closing operation of the chopper is not particularly limited, and a suitable drive method may be selected depending on the kind of the chopper. In the case where the chopper is a combination of a deflection electrode and an aperture, the opening and closing operation of the chopper can be performed with satisfactory accuracy by supplying a voltage to the deflection electrode through use of a waveform generator. Further, a voltage application signal to the deflection electrode can be branched and sent to a mass spectrometer as a trigger signal at the same time or at time delayed by predetermined time through a delay time generation device. In this case, the chopping operation by the chopper and secondary ion measurement by the mass spectrometer can be coordinated with satisfactory accuracy.
When the sample is irradiated with the second ion group, the sample may be irradiated with and scanned by a converged secondary ion group (scanning type), or a specified region of the sample may be irradiated with a secondary ion group collectively (projection type).
In the case of the scanning type, the ion group for irradiation is converged through use of a converging electrode and further deflected through use of a deflection electrode, an thus a minute region on the sample is irradiated with and scanned by the ion group. The irradiation diameter is not limited, but is preferably about 0.01 μmφ to 50 μmφ considering that the irradiation diameter directly influences the spatial resolution of a mass image obtained by secondary ion mass spectrometry.
In the case of the projection type, the irradiation diameter for irradiation of the ion group is converged or enlarged through use of a converging electrode, and the ion group is deflected through use of a deflection electrode, as needed, and thus a specified region of the sample is irradiated with the ion group collectively. The irradiation diameter in the projection type is not particularly limited, but is preferably about 0.01 mmφ to 10 mmφ because this diameter corresponds to the area of a measurement region.
In the present invention, the sample is irradiated with two or more second ion groups, e.g., groups formed of ions having different average masses and including an atom species or molecule species common between the ion groups. As illustrated in
As the mass of ions serving as primary ions forming the second ion group becomes larger, fragmentation of sample molecules is suppressed more, and hence precursor ions tend to be obtained as secondary ions. On the other hand, when the mass is too large, a secondary ion spectrum may not be obtained easily in some cases. The mass of ions serving as primary ions for forming the second ion group can be selected appropriately in accordance with the molecular weight of molecules forming a target region, in particular, precursor ions (or fragment ions) to be focused.
The difference in mass of constituent ions between the second ion groups, is not particularly limited. However, when the mass difference of primary ions is too small, the difference of secondary ion spectra to be obtained is not likely to be obtained in some cases. Therefore, the difference in mass of constituent ions between the ion groups is preferably 100 or more, more preferably 500 or more, still more preferably 2,000 or more.
The sample 24 is a solid or a liquid, and includes an organic compound, an inorganic compound, or a biological sample or the like. An example of fixing the sample is fixing the sample to the flat substrate 25 and holding the sample on the sample holding unit 26.
The material for the substrate 25 is not limited, and a metal such as gold, ITO, or silicon or glass whose surface is coated with the metal or ITO is preferably used from the viewpoint of suppressing charging of the sample 24 involved in primary ion irradiation and secondary ion release.
The sample holding unit 26 includes a region for holding the sample 24 and the substrate 25, and further may include a Faraday cup for measuring a current value of the ion group with which the sample 24 is irradiated. Further, the sample holding unit 26 may include a temperature adjustment mechanism for heating or cooling the sample.
It is preferred that the sample holding unit 26 be moved or rotated in a horizontal direction or moved in a height direction. A region and height for irradiation of primary ions can be adjusted through the control in an in-plane direction and a height direction. Further, it is preferred that the sample holding unit 26 can also be inclined. An incident angle of primary ions with respect to a sample surface can be controlled through the control of inclination. Although primary ions may enter the sample surface coaxially or at different incident angles for each ion group, it is preferred that the ions enter the sample surface coaxially.
How many times the sample is irradiated with the ion group, e.g., the second ion group (number of ion groups for irradiation) is not particularly limited. In the case where the same region of the same sample is irradiated with the second ion group multiple times, the operation can also be finished before the ion amount to be irradiated reaches a static limit or more. The static limit refers to a level at which the phenomenon that ions strike a position once and other ions strike the same position again is negligible according to theory of probability. The ion irradiation amount in this case is 1% or less of atoms and molecules forming the surface.
The number of irradiations of each ion group and the order thereof are not particularly limited. The number or order of irradiations of the second ion groups for each kind may be on a random basis or on a regular basis. As an example, the following pattern is considered: (a) the number and order of irradiations are random for each kind of ion groups; (b) the kind of the ion group is the same at a specified number of time and the other is random; (c) the number and order of irradiations have a specified rule for each sequence, which is repeated; and (d) multiple sequences are repeated randomly or regularly.
Secondary ions generated from a sample surface which is irradiated with ion groups are measured by a mass spectrometer. The mass spectrometer includes an extraction electrode for extracting secondary ions in the vicinity of the sample, a mass separation portion for separating the secondary ions extracted by the extraction electrode based on a mass-to-charge ratio, and a detector for detecting each separated secondary ion.
Further, the mass spectrometer may include, besides the mass separation portion, a secondary ion group selecting mechanism for selecting only a part of the generated secondary ions as the secondary ion group. The time width of secondary ions can be shortened by selecting only a part of the generated secondary ions as the secondary ion group, and hence the mass resolution in a secondary ion mass spectrum to be obtained can be enhanced. Note that, the secondary ion group selecting mechanism may have a function of selectively separating secondary ions based on a mass.
The secondary ion group selecting mechanism may be provided in the extraction electrode or in another component. In the case where the secondary ion group selecting mechanism is provided in the extraction electrode, the secondary ion group can be selected, for example, by shortening a time width of charge application. In the case where another component is used, the a secondary ion group may be selected by setting a secondary ion group selecting electrode between the extraction electrode and the mass separation portion and controlling voltage application to the secondary ion group selecting electrode. For example, in an orthogonal time-of-flight mass spectrometer, the secondary ion group selecting electrode is provided between the extraction electrode and the mass separation portion, and the mass separation portion is provided in a direction perpendicular to the traveling direction of secondary ions directed from the extraction electrode to the secondary ion group selecting electrode. In this case, the extraction electrode constantly extracts the secondary ions and repeats ON/OFF of the voltage application to the secondary ion group selecting electrode, with the result that a part of the extracted secondary ions can be selected as the secondary ion group, and simultaneously the secondary ion group can be introduced into the mass separation portion.
A mass separation system in the mass spectrometer is not particularly limited, and various systems such as a time-of-flight type, a magnetic deflection type, a quadrupole type, an ion-trap type, a Fourier transform ion cyclotron resonance type, an electric field Fourier transform type, and a multiturn type can be used alone or in combination.
In the case where the sample is irradiated with the ion group by the projection type, mass information and detection position information of the secondary ions can be recorded simultaneously by using the mass spectrometer including the detector having a two-dimensional ion detection function.
In the case where the sample is irradiated with the ion group by the scanning type, position information is recorded at a time of irradiation of the ion group. In this case, only a mass-to-charge ratio of the secondary ions needs to be measured, and hence a detector suitable for each mass spectrometric system may be used.
In the case where the sample is irradiated with the ion group by the scanning type, the mass spectrometer does not need to detect position information and only needs to measure a mass-to-charge ratio of the secondary ions. Therefore, a detector suitable for each mass spectrometry system may be used.
The result of mass spectrometry is analyzed by the analysis device and can be output from the output device as analyzed secondary ion mass spectrum and mass distribution image. The analysis device and output device may be integrated circuits or the like having a dedicated arithmetic operation function and a memory, or may be constructed as software in a general-purpose computer.
Analysis can be performed based on multiple secondary ion mass spectra obtained for each kind of irradiated primary ions. For analysis, each spectrum having each position information in an irradiation region may be used, and a spectrum obtained by accumulating a predetermined region in the irradiation region may be used. The analysis may include a division process of one secondary ion mass spectrum, calibration of a mass-to-charge ratio, and accumulation, averaging, and normalization of mass spectra obtained through irradiation of ion groups of the same kind.
An analysis method of analyzing a difference among multiple secondary ion mass spectra is not particularly limited. Various processing methods such as general processing (addition, subtraction, balancing, division, and accumulation using multiple different spectra), or analysis processing based on a gentle SIMS (G-SIMS) method can be performed alone or in combination.
In another embodiment, the average mass of ions vary for each ion group, but ions of each ion group include an atom species or molecule species common between the ion groups. Thus, the ion groups have similar chemical properties other than an average mass and are unlikely to vary due to a chemical reaction, with the result that the ion groups are advantageous for integrating spectra.
The sputtering efficiency and the occurrence probability of fragmentation mainly depend on the average mass of primary ions. On the other hand, the reactivity of a chemical reaction has specificity depending on a combination of primary ions and a sample molecule species. Primary ions contributing to a reaction are decomposed when they reach a sample surface, and hence an atoms species or a molecule species forming primary ions substantially determine the reactivity. Therefore, even in the case where primary ions have different average masses, the reactivity with respect to sample molecules is similar as long as an atom species or molecule species forming the primary ions is common between the primary ions, and hence the generation of specific secondary ions is suppressed. Thus, in the present invention, when an atom species or molecule species forming the primary ions is common between the primary ions, even in the case where the primary ions have different average masses, the generation of secondary ions of specific kind or amount dependent on an ion species can be suppressed, and multiple secondary ion mass spectra can be subjected to difference analysis with satisfactory accuracy.
Further, when an atom species or molecule species forming primary ions is common between the primary ions, signals derived from the primary ions included in secondary ions are similar to each other, and hence multiple secondary ion mass spectra can be subjected to difference analysis with satisfactory accuracy.
For the above-mentioned reasons, in the present invention, as the ions forming two or more ion groups serving as primary ions, ions including an atom species or molecule species common between the ion groups can be used preferably. More preferably, the above-mentioned ions include an atom species or molecule species which is identical between the ion groups. Still more preferably, the above-mentioned ions have an equal configuration ratio of an atom species or molecule species between the ion groups. Each specific example is shown below.
<Example of ions including common atom species or molecule species>
(i) [(H2O)n]+ and (ii) [(H2O)m(CH3OH)q]+ (n=1 to 100,000, m=1 to 100,000, q=1 to 100,000)
<Example of ions including same atom species or molecule species>
<Example of ions including same atom species or molecule species in which configuration ratio of atom species or molecule species is equal>
(i) [(H2O)n(CH3(OH)p)]+ and (ii) [(H2O)m(CH3OH)r]+ (n=1 to 100,000, m=1 to 100,000, p=1 to 100,000, r=1 to 100,000, provided that n and m are not equal to each other, p and r are not equal to each other, and an n/m ratio is equal to a p/r ratio). Note that, the present invention is not limited to those examples.
The average mass of ions included in an ion group is not particularly limited. As the mass of primary ions is larger, fragmentation of sample molecules is suppressed more, and hence precursor ions tend to be obtained as secondary ions. On the other hand, when the mass is too large, a spectrum may not be obtained easily in some cases. The mass of an ion group can be selected appropriately in accordance with the molecular weight of molecules forming a target region, in particular, precursor ions (or fragment ions) to be focused.
An example of the difference analysis for multiple obtained secondary ion mass spectra is described. The difference analysis uses the following: as the mass of primary ions to be irradiated is larger, fragmentation of sample molecules can be suppressed more and precursor ions are more likely to be obtained.
Note that, the precursor ions refer to ions (M+) obtained when sample molecules (M) are ionized through the removal of electrons and ions (M−) obtained when sample molecules (M) are ionized through the addition of electrons, and ions obtained when sample molecules (M) are ionized through the addition or removal of specified electrons in which fragmentation has not occurred. Typical examples of ions to be generated by the addition or removal include protonated ions ([M+H]+), deprotonated ions ([M−H]+, [M−H]−), sodium adduct ions ([M+Na]+), potassium adduct ions ([M+K]+), ammonium adduct ions ([M+NH4]+), and chlorine adduct ions ([M+Cl]−). Besides those, the typical examples also include adducts of metal ions, ions derived from a primary ion species, and ions derived from a matrix around sample molecules.
Further, a mass distribution image in which precursor ions and fragment ions are clearly discriminated from each other can also be obtained based on a secondary ion mass spectrum in which precursor ions and fragment ions are clearly distinguished from each other.
As described above, the sample can be irradiated with two or more ion groups having different average masses of ions forming the ion groups in a short period of measurement time by the secondary ion mass spectrometer of the present invention. Thus, two or more different secondary ion mass spectra can be obtained in a short period of time, and hence the peak distinction between precursor ions and fragment ions and the identification of a sample molecule species can be performed with satisfactory throughput.
Moreover, as described above, in the secondary ion mass spectrometer of the present invention, a sample can be irradiated with multiple kinds of ion groups having different masses without limiting an ion species to be used. A peak of a precursor ion can be distinguished from a peak of a fragment ion based on the difference between multiple kinds of secondary ion mass spectra to be obtained, and hence it becomes easy to identify a sample molecule.
The configuration of this embodiment is described with reference to
In this embodiment, the ion group selecting unit 28 includes a first chopper 38 positioned on the ion source side, a second chopper 40, and an ion separator 39 disposed between the first and second choppers 38, 40. The first and second choppers 38, 40 perform a chopping operation of selecting an ion group by changing from a closed state to an opened state for a predetermined period of time, thereby passing ions in a traveling direction only for the predetermined period of time, e.g., by passing and blocking ions in a traveling direction through opening and closing. Thus, The first and second choppers each perform a chopping operation of selecting an ion group by passing and blocking ions in a traveling direction through opening and closing.
In one embodiment, the second chopper 40 has a feature of performing two or more chopping operations for one chopping operation by the first chopper 38.
Ions released from the ion source include various kinds of ions and form an ion aggregate having an infinite time width or a large time width. The time width of the ion aggregate refers to a width of a time period during which ions are released from the ion source. The ion aggregate first reaches the first chopper 38 and is selected as the first ion group including ions having a small time width and various masses by the chopping operation of the first chopper 38. Next, the first ion group is further separated by the ion separator 39, and then subjected to two or more chopping operations by the second chopper 40. As described above, two or more second ion groups having a small time width, less mixed ions other than target ions, and different masses can be obtained in a short period of time.
As described above, when the first chopping operation, ion separation, and second chopping operation are performed, an ion group having a small time width and less mixed ions other than target ions can be obtained easily. When an ion group has a small time width and less mixed ions other than target ions, the enlargement of the time width of the ion group up to the time when the ion group reaches the sample surface can be reduced, and hence the mass resolution of generated secondary ions can be enhanced. Therefore, the first chopper 38, the second chopper 40, and the ion separator 39 disposed between the first and second choppers 38, 40 can be used preferably.
In another example, the second chopper performs one chopping operation in coordination with one chopping operation by the first chopper. In a specified cycle in which the chopping operations by the first chopper and the second chopper are repeated multiple times, there are multiple differences between the opening time of the first chopper and the opening time of the second chopper.
A large ion group including ions having various masses released from the ion source and having an infinite or large time width first reaches the first chopper 38 and is selected as a medium ion group including ions having a small time width and various masses by the chopping operation by the first chopper 38. Next, the medium ion group is further separated by the ion separator 39, and finally an ion group having less mixed ions other than target ions and having a small time width and a specified average mass is obtained by the second chopper 40. As described above, when the first chopping operation of the large ion group including ions of multiple masses, the separation, and the second chopping operation are performed, an ion group formed of ions having the small time width, a small mass width in a mass distribution, and a specified average mass can be obtained.
The other configurations are the same as those of the first embodiment.
The configuration of this embodiment is described with reference to
This embodiment of the present invention has a feature in that the ion separator is a time-of-flight mass separator. In one example, the first and second choppers perform chopping operations of selecting an ion group by passing and blocking ions in a traveling direction through opening and closing, and the second chopper performs one chopping operation in coordination with one chopping operation by the first chopper. In a particular cycle in which the chopping operations by the first and second choppers are repeated multiple times, there can be multiple differences between the opening time of the first chopper and the opening time of the second chopper.
The time-of-flight mass separator 41 has high mass resolution. In addition, a parameter to be controlled for separating ions into an ion group is only a time difference due to the use of the time-of-flight mass separator 41, and hence the convenience and accuracy of control are enhanced. As described above, an ion group having high mass resolution and high mass accuracy is obtained easily, and hence the above-mentioned apparatus can be used preferably.
The operation of
An example of a timing chart of opening and closing of the chopper according to this embodiment is described with reference to
As illustrated in
A timing chart 46 of the first chopper 38 of
A timing chart 125 of the first chopper of
The difference between the opening time of the first chopper 38 and the opening time of the second chopper 40 is not particularly limited and may be set randomly or in an intended manner. For example, the second chopper 40 may be operated in accordance with the time difference in which ions having a specified mass pass through the second chopper for the purpose of irradiating a sample with the ions having the specified mass.
Note that, a period of time from the time when the ions having a specified mass-to-charge ratio pass through the first chopper 38 to the time when the ions reach the second chopper 40 can be calculated as delay time (time-of-flight time). That is, a period of time “t” during which ions having a mass “m” and a charge number “z” flying with an acceleration voltage V fly through a flight-path length having a total length L at an equal speed can be obtained by Expression (1).
t=L(m/2zeV)½ (1)
where “e” represents an elementary charge.
The difference between the opening time of the first chopper 38 and the opening time of the second chopper 40 for passing ions having a specified mass can be determined by applying, to Expression (1), the flight-path length L as the length of the time-of-flight mass separator 41 or as a distance between the first chopper 38 and the second chopper (in the case where the time-of-flight mass separator is not provided separately from a device barrel and a potential is provided based on a ground potential). Note that, the mass resolution is enhanced as the flight-path length is larger. However, the flight-path length is preferably about 0.1 m to 1 m from the viewpoint of the throughput and constraint of a space.
Although the opening period of time of the first chopper 38 is not particularly limited, the opening period of time is in a range of about 0.5 nsec to 50 μsec. The opening period of time of the first chopper 38 influences the mass resolution in the later time-of-flight mass separator, and hence may be determined considering various parameters such as a time-of-flight length and an acceleration voltage and desired mass resolution of primary ions. The opening period of time of the first chopper 38 may be constant or vary for each cycle. The variation may be made on a random basis or on a regular basis.
Although the opening period of time of the second chopper 40 is not particularly limited, the opening period of time is in a range of about 0.5 nsec to 50 μsec. Note that, the opening period of time may influence the mass resolution of secondary ions emitted from the sample by the irradiation of primary ions. That is, when the time width of an ion group of primary ions is too large, the uncertainty about the time when secondary ions are generated increases, which may degrade the mass resolution in some cases. On the other hand, as the mass-to-charge ratio of primary ions becomes larger, the period of time up to a time when the primary ions pass through the second chopper 40 becomes longer, and an opening period of time is set to be longer. Considering the foregoing, the opening period of time may be determined. The opening period of time of the second chopper 40 may be constant or vary for each cycle. The variation may be made on a random basis or on a regular basis.
Further, the difference between the opening time of the first chopper and the opening time of the second chopper is not particularly limited, but is desirably about 0.1 μsec to 1,000 μsec.
The opening times, opening periods of time, and opening intervals of the first and second choppers may vary on a random basis or on a regular basis. In the case of performing a regular operation, as illustrated in
Further, the second chopper may repeat an opening and closing operation two or more times during an opening interval of the first chopper. The operation of the second chopper in this case may or may not be performed at a constant interval.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, in the primary ion irradiation unit, a combination of one chopping operation by the first chopper and two or more chopping operations by the second chopper coordinated with the chopping operation by the first chopper is defined as one cycle. At this time, the sample is successively irradiated with two or more second ion groups selected from at least one cycle in the order from second ion groups including ions having a smaller mass.
In the case of using a time-of-flight mass separator as the ion separator, in one cycle, the second ion groups are selected successively from those including ions having a smaller mass. Therefore, in the case where the sample is irradiated with the second ion groups successively from those including the ions having a smaller mass, it is not necessary to exchange the order of the ion groups between the ion selection and the irradiation. Thus, a time of period from the selection of ions to the irradiation thereof can be shortened most regarding each ion group.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, as the mass spectrometer for measuring secondary ions generated from the sample, a time-of-flight mass spectrometer is used.
The time-of-flight mass spectrometer guides all the secondary ions generated from the sample to an extraction electrode and accelerates the secondary ions at an acceleration voltage V, and thereafter allows the secondary ions to fly through a free space having the flight-path length L to reach a detector. The secondary ions are separated for each mass-to-charge ratio, and hence the mass “m” of each secondary ion can be determined based on Expression (1) by measuring the arrival time “t” of the ions to the detector.
The time-of-flight mass spectrometer is capable of performing high-sensitivity analysis due to its high transmittance of ions. Moreover, the time-of-flight mass spectrometer has high mass resolution and facilitates the separation between peaks, and hence the distinction between the precursor ions and the fragment ions is rendered easy. The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, in irradiation of two or more second ion groups to the sample, the irradiation of each second ion group is measured by the mass spectrometer. One measurement is performed for one irradiation, and hence the measurement time of a secondary ion spectrum can be varied depending on the mass of the second ion group to be irradiated.
For example, as the mass of ions forming the second ion group becomes larger, the measurement time of the secondary ion spectrum can be rendered longer.
In this case, as illustrated in
The measurement time of the time-of-flight mass spectrometer depends on the mass range to be measured. As the mass of secondary ions becomes larger, the arrival time of ions to the detector becomes longer based on Expression (1). Therefore, measurement takes time. On the other hand, as the mass of primary ions becomes smaller, secondary ions having a large mass are unlikely to be generated, and measurement may be sufficient in some cases in a range of a small mass. Thus, as the mass of ions forming the ion group to be irradiated becomes smaller, the measurement time of secondary ions can be shortened.
In this embodiment, the measurement time of secondary ions can be changed in accordance with the mass of primary ions. Therefore, even in the case where the sample is irradiated with two or more ion groups, the measurement time for one cycle can be made shortest, and the measurement time of the entire cycle can also be shortened. This is effective, in particular, in the case of using the time-of-flight mass separator for selecting the second ion groups. For example, in the case of using the separator, it takes long time for selecting ion groups formed of ions having a large mass. However, as illustrated in
Note that, measurement start times 56, 58 of secondary ions are not particularly limited and may be coordinated with the opening time or the closing time of the second chopper 40. Further, measurement end times 57, 59 and measurement time periods of secondary ions are not particularly limited, and may be determined based on any of an arbitrary measurement time period, mass of ions forming the second ion groups to be irradiated, an arbitrary measurement mass range, and the next opening time or closing time of the second chopper 40 (in
Note that, there is no limit to the difference in mass of ions forming two or more ion groups to be irradiated. Note that, in the case where the time-of-flight mass separator is used for selecting the second ion group, and the time difference for irradiation is the same as that for selection, a time difference is unlikely to be obtained between ion groups if the masses are close to each other, and hence the detection time periods of secondary ion spectra may overlap each other in some cases. Therefore, in this embodiment, in the case where the time-of-flight mass separator is used for selecting the second ion group, and the time difference for irradiation is the same as that for selection, the difference between the masses is preferably 1,000 or more, more preferably 10,000 or more.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, the opening time or closing time in the chopping operation of the second chopper 40 is used as the measurement start time of the time-of-flight mass spectrometer.
In the present invention, the measurement start time of the time-of-flight mass spectrometer is not particularly limited. Note that, the measurement operation can be simplified and controlled easily through use of the opening time or closing time in the chopping operation of the second chopper 40.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, the opening time and closing time in the chopping operation of the second chopper 40 are used as the measurement start time of the time-of-flight mass spectrometer.
In the present invention, the measurement start time and the measurement end time (that is, measurement time period) of the time-of-flight mass spectrometer are not particularly limited. Note that, in the case where a measurement operation by the time-of-flight mass spectrometer is performed for each irradiation of the second ion group, the measurement operation can be simplified and controlled easily through use of the closing time in the chopping operation of the second chopper 40 as the measurement start time of the time-of-flight mass spectrometer and through use of the opening time in the chopping operation of the second chopper 40 as the measurement endtime of the next time-of-flight mass spectrometer. In addition, the measurement time of secondary ions can be kept longest with respect to the irradiation of each second ion group, and hence a secondary ion spectrum having a largest mass range can be obtained.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, the mass spectrometer performs one measurement operation in one cycle.
In this embodiment, secondary ion spectra obtained thorough the irradiation of two or more ion groups are obtained as one secondary ion spectrum. Note that, the secondary ion spectra corresponding to the kinds of ion groups to be irradiated are sufficiently separated from each other in terms of time. Therefore, two or more different secondary ion spectra corresponding to the kinds of ion groups to be irradiated can be obtained by dividing the above-mentioned one secondary ion spectrum.
Note that, a measurement start time 62 of secondary ions is not particularly limited and may be coordinated with the opening time or closing time of the second chopper 40. Further, a measurement end time 63 and measurement time period of secondary ions are not particularly limited and may be determined based on any of an arbitrary measurement time period and the next opening time or closing time of the first chopper 38 (in
There is no limit to the difference between masses of ions forming the two or more ion groups to be irradiated. Note that, in this embodiment, in the case where the time-of-flight mass separator is used for selecting the second ion group, and a time difference for the irradiation is the same as that for selection, a time difference is unlikely to be obtained between ion groups when the masses are close to each other, and secondary ion spectra may not be separated for each ion group in some cases. Therefore, in the case where the time-of-flight mass separator is used for selecting the second ion group, and a time difference for irradiation is the same as that for selection, the difference in mass is preferably 1,000 or more, more preferably 10,000 or more.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, an opening time or a closing time in the chopping operation performed by the second chopper 40 conducted at the earliest time in one cycle is used as a measurement start time of the time-of-flight mass spectrometer.
In the present invention, the measurement start time of the time-of-flight mass spectrometer is not particularly limited. Note that, in the case where one measurement is performed by the time-of-flight mass spectrometer in one cycle, the measurement operation can be simplified and controlled easily through use of the timing of the chopping operation by the second chopper 40 performed at the earliest time in one cycle as the measurement start time of the time-of-flight mass spectrometer.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, a closing time in the chopping operation performed by the second chopper 40 conducted at the earliest time in one cycle is used as a measurement start time of the time-of-flight mass spectrometer, and an opening time in the chopping operation performed by the second chopper 40 conducted at the earliest time in next one cycle is used as a measurement end time of the time-of-flight mass spectrometer.
In the present invention, the measurement end time of the time-of-flight mass spectrometer is not particularly limited in each cycle.
In the present invention, the measurement start time of the time-of-flight mass spectrometer is not particularly limited. Note that, in the case where one measurement operation is performed by the time-of-flight mass spectrometer in one cycle, the measurement operation can be simplified and controlled easily through use of the closing time in the chopping operation performed by the second chopper 40 conducted at the earliest time in one cycle as the measurement start time of the time-of-flight mass spectrometer, and through use of the opening time in the chopping operation performed by the second chopper 40 conducted at the earliest time in next one cycle as the measurement end time of the time-of-flight mass spectrometer. In addition, the measurement time of secondary ions can be kept longest with respect to the irradiation of two or more second ion groups in one cycle, and hence a secondary ion spectrum having a largest mass range can be obtained.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, at least one of two or more second ion groups is formed of cluster ions. The use of cluster ions can suppress the fragmentation of sample molecules. Therefore, precursor ions can be detected at high sensitivity even with respect to sample molecules having a large mass and can be distinguished from the fragment ions easily.
The range of a cluster size of cluster ions to be used is not particularly limited and may be arbitrarily determined based on the mass range of target molecules. In general, as a cluster size increases, precursor ions can be detected with satisfactory sensitivity even with respect to molecules having a large mass.
Note that, the cluster size can be calculated through use of the mass of ions forming the ion group.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, an ion material for ions forming at least one ion group of two or more second ion groups contains any one of a gas, a liquid, and a mixture of a gas and a liquid at normal temperature and normal pressure. In the present invention, the kind of the ion material is not particularly limited. However, cluster ions having a larger cluster size can be generated by using a gas or a non-metal liquid as the ion material rather than by using a liquid metal. As the cluster size increases, precursor ions can be detected with high sensitivity even with respect to molecules having a large mass. Therefore, it is preferred that the ion material contain any one of a gas, a liquid, and a mixture of a gas and a liquid at normal temperature and normal pressure.
Examples of the gas at normal temperature and normal pressure include: rare gases such as argon and xenon; and oxygen. Note that, the present invention is not limited thereto.
Examples of the liquid at normal temperature and normal pressure include water, an acid, an alkali, and an organic solvent such as an alcohol. Note that, the present invention is not limited thereto.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, at least one of the two or more second ion groups contains one kind of molecule of water, an acid, and an alcohol. In the present invention, a constituent atom species or molecule species of ions forming an ion group is not particularly limited. However, when a sample is irradiated with primary ions containing at least one kind of water, an acid, and an alcohol, molecules having a proton affinity such as biological molecules can be accelerated to generate proton adduct ions. As a result, the detection sensitivity of precursor ions of the molecules is enhanced. Therefore, it is preferred that at least one of the two or more second ion groups contain water molecules containing at least one kind of water, an acid, and an alcohol.
There is no particular limit to ions containing water molecules, and preferred examples thereof include [(H2O)n]+(n=1 to 100,000) and [(H2On+mH)m+ (n=1 to 100,000, m=1 to 100,000).
An example using the following two ion groups is described below: an ion group in which water molecules are formed of 10±2 water cluster ions ([(H2O)10±2]+); and an ion group in which water molecules are formed of 1,000±20 water cluster ions ([(H2O)1000±20]+). Note that, [(H2O)10±2]+ refers to ions obtained as a result of an error of ±2 in selecting an ion group although an average of the numbers of water molecules included in ions is 10. Similarly, [(H2O)1000±20]+ refers to ions obtained as a result of an error of ±20 in selecting an ion group although an average of the numbers of water molecules included in ions is 1,000.
Water cluster ions can be obtained by heating water serving as an ion material with the ion material supply unit, spraying the heated water in a vacuum, and subjecting the neutral water cluster thus formed to electron impact ionization. A part of an aggregate of ionized ions having multiple cluster sizes is selected as an ion group with the first chopper 38. The ion group is subjected to mass separation with the time-of-flight mass separator. After the elapse of a specified time period ΔT1 from the chopping operation by the first chopper 38, the second chopper 40 performs a chopping operation to select an ion group formed of [(H2O)10±2]+. A sample containing biological molecules is irradiated with the selected ion group formed of [(H2O)10±2]+. Secondary ions from the irradiated surface are subjected to mass spectrometry for the measurement time period Δt1 by the time-of-flight mass spectrometer. Next, after the elapse of a specified time period ΔT2 from the chopping operation by the first chopper 38 (ΔT1+Δt1<ΔT2), the second chopper 40 performs a chopping operation to select an ion group formed of [(H2O)1000±20]+. The sample containing biological molecules is irradiated with the selected ion group formed of [(H2O)1000±20]+. Secondary ions from the irradiated surface are subjected to mass spectrometry for the measurement time period Δt1 with the time-of-flight mass spectrometer. Thus, two kinds of secondary ion mass spectra can be obtained within a short period of time. A precursor ion peak of biological molecules is obtained with satisfactory sensitivity in the two kinds of obtained spectra. Therefore, the distinction of precursor ions and the identification of biological molecule species are performed easily by comparison analysis processing. Note that, the present invention is not limited to the above-mentioned example.
The kind of the acid is not particularly limited, and preferred examples thereof include formic acid, acetic acid, and trifluoroacetic acid.
The kind of the alcohol is not particularly limited, and preferred examples thereof include methanol, ethanol, and isopropyl alcohol.
There is no particular limit to the number and ratio of water, acid, and alcohol molecules included in one ion group. Note that, as the number of the molecules is larger, a protonation ratio is enhanced in some cases.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, at least one of two or more second ion groups includes rare gas molecules. In the present invention, a constituent atom species or molecule species of ions forming the two or more ion groups is not particularly limited. However, when the sample is irradiated with primary ions including rare gas molecules, the contamination of the sample surface involved in the irradiation of primary ions can be prevented because the reactivity of the rare gas molecules is low. Therefore, it is preferred that at least one of the two or more second ion groups include rare gas molecules.
Although there is no particular limit to the kind of the rare gas molecules, argon or xenon can be preferably used from the viewpoint of a mass and cost.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, the mass spectrometer for measuring secondary ions includes a detector having a two-dimensional ion detection function of detecting secondary ions generated from the sample surface while keeping a positional relationship at a secondary ion generation position.
When the mass spectrometer including the detector having the two-dimensional ion detection function is used, the generation position of secondary ions on the sample surface can be recorded, and hence it is not necessary to scan primary ions. Therefore, a target region on the sample can be irradiated with primary ions simultaneously, and secondary ions at each position in the target region can be detected collectively. Consequently, compared to the case of scanning primary ions, measurement can be completed within a short period of time.
The mass spectrometer of this embodiment may include a projection adjusting electrode for adjusting a projection magnification besides an extraction electrode, a mass separation portion, and the above-mentioned detector. The projection adjusting electrode has a function of enlarging or reducing a spatial distribution of secondary ions on a two-dimensional plane perpendicular to the traveling direction of secondary ions directed to the detector.
Secondary ions generated from the sample surface due to the irradiation of the ion group are extracted by the extraction electrode supplied with a voltage of several to several 10 kV. Next, the extracted secondary ions are enlarged or reduced by any projection magnification with the projection adjusting electrode and introduced into the mass separation portion. Then, the introduced secondary ions are separated based on a mass-to-charge ratio and further enlarged or reduced as needed. In the above-mentioned process, the relative positional relationship of the secondary ions on the sample surface is kept. The separated secondary ions are successively detected with the detector, and the mass information and two-dimensional position information are recorded.
Although the mass separation system in the mass spectrometer in this embodiment is not particularly limited, for example, the detection time (corresponding to the mass of secondary ions) and detection position of secondary ions can be recorded simultaneously through use of a time-of-flight mass separation system.
There is no particular limit to the kind of the detector having the two-dimensional ion detection function, and a detector having any configuration can be used as long as the detector can detect a time and a position at which ions are detected. For example, any one of a combination of a micro-channel plate (MCP) and a two-dimensional electron position detector (for example, a delay line detector), a combination of the MCP and a fluorescent plate, a combination of the MCP and a charge-coupled device (CCD) two-dimensional detector, and a detector in which minute MCPs are arranged two-dimensionally can be used.
When secondary ions are measured through use of the mass spectrometer in this embodiment, the sample is irradiated with the ion group by the projection type, and secondary ions generated from a whole or a part of an irradiation region are measured. The irradiation position and area of the ion group can be determined arbitrarily based on the ion current amount, incident angle, distance between the sample surface and the ion irradiation unit, and the like through use of the primary ion irradiation device. The area and projection magnification of a secondary ion measurement target region can be determined arbitrarily based on the distance between the extraction electrode and the sample, voltage applied to the extraction electrode, voltage applied to the projection adjusting electrode, and the like.
When secondary ions are measured through use of the mass spectrometer in this embodiment, the secondary ions may be measured continuously or discretely for one ion group irradiation. In the case where the secondary ions are measured discretely, a mass distribution image of target molecules can be obtained at a high speed by controlling a measurement timing in accordance with the mass information of the target molecules.
The other configurations are the same as those of the above-mentioned embodiments.
This embodiment has a feature of including an intermittent valve for supplying an ion material. In the present invention, there is no particular limit to the structure of the ion material supply unit. However, when an ion material is supplied intermittently through use of the intermittent value, a load of a vacuum discharge system can be reduced compared to the case of supplying the ion material continuously. Therefore, in the present invention, the intermittent value is preferably used.
The intermittent valve refers to a valve including an opening and having a function of repeating opening and closing intermittently. The intermittent valve may have a function of not completely closing the opening even in a closed state. Note that, it is preferred that the opening be completely closed in the closed state from the viewpoint of vacuum maintenance in a jetting space.
There are the following kinds of intermittent valves in terms of a valve disc structure: a gate valve, a glove valve, a ball valve, a butterfly valve, a needle valve, and a diaphragm valve. Further, there are the following kinds of intermittent valves in terms of a valve disc drive system: an electromagnetic valve, an electric valve, an air valve, and a hydraulic valve. As the intermittent valve of the present invention, any kind can be used. Note that, the electromagnetic valve is preferably used from the viewpoint of a response speed. Examples of the electromagnetic valve include a poppet type, a spool type, and a slide type in terms of an opening/closing mechanism of a valve seat, and any kind may be used.
There is no particular limit to a drive method of an opening and closing operation of the intermittent valve, and any suitable drive method may be selected depending on the kind of the intermittent valve. In the case where the intermittent valve is an electromagnetic valve, the opening and closing operation of the intermittent valve can be performed with satisfactory accuracy by supplying a voltage through use of a waveform generator. Further, a voltage application signal to the intermittent valve can be branched and sent to the chopper as a trigger signal at the same time or times delayed by a predetermined period of time via a delay time generation device. In this case, the jetting operation of the ion material by the intermittent valve and the chopping operation by the chopper can be coordinated with each other with satisfactory accuracy.
The other configurations are the same as those of the above-mentioned embodiments.
This embodiment has a feature in that the number of times of irradiation of the two or more ion groups are respectively determined based on ion current values of the respective ion groups. The ion current value is measured as a value of a current flowing through a target when the target is irradiated with an ion group. The current value is a charge amount per unit time, and hence corresponds to the number of ions with which the sample is irradiated by one specified ion group. When an ion current value of a specified ion group out of multiple ion groups is small, the number of ions with which the sample is irradiated per ion group is small, and hence the number of secondary ions to be generated from the sample also becomes small. Consequently, the intensity of the obtained secondary ion mass spectrum becomes small as a whole and may not be sufficiently compared to mass spectra obtained by the irradiation of the other ion groups in some cases. In this embodiment, the number of irradiations can be set to be larger in advance, for example, with respect to an ion group having a small ion current value. That is, in this embodiment, the difference in spectrum caused by the difference in ion group is reduced, and mass spectra of secondary ions which can be compared to each other are obtained.
Although the relationship between the ion current value and the number of irradiations is not particularly limited, it is preferred that the number of irradiations be determined so that the product of an ion current value and the number of irradiations of each kind of ion groups becomes a difference within one order of magnitude for each ion group.
The ion current value may be obtained by directly measuring a current value of the second ion group or by calculating the ion current value based on a current value of a continuous ion beam before being selected to a second ion group.
In the case of directly measuring the current value of the second ion group, a micro-channel plate (MCP) is irradiated with the second ion group to obtain a mass spectrum, and a peak area value thereof is used.
On the other hand, in the case of calculating the ion current value based on the current value of the continuous ion beam, first, the sample holding mechanism or another portion in the device is irradiated with the continuous ion beam, and a current value thereof is measured. More preferably, the Faraday cup included in the sample holding mechanism is irradiated with the continuous ion beam, and a current value thereof is measured. Next, the ion current value is calculated through use of the measured current value and a duty ratio (time width of the second ion group/time interval for selecting the second ion group) for selecting the second ion group from the continuous ion beam.
The ion current value obtained as described above regarding each second ion group is fed back to setting conditions for determining the number of irradiations of the ion group irradiation device. The product of the ion current value and the number of irradiations becomes a total charge amount with which the sample is irradiated, and hence the number of irradiations can be determined based on an obtained ion current and setting of the total charge amount.
The measurement and calculation of the ion current, and the determination of the number of irradiations by the feedback of the measurement and calculation may be performed manually by a measurer or may be performed automatically by a device.
The other configurations are the same as those of the above-mentioned embodiments.
In this embodiment, a change in ion current value or cluster size of the second ion group with which the sample is irradiated is monitored, and the monitored change is fed back to setting conditions of the device so that the change is suppressed.
In the case where the selection and irradiation of an ion group are performed for a long period of time, a current value and a cluster size of the ion group may change even when the setting conditions of the device are the same during the selection and the irradiation. In this case, measurement results vary for each cycle in which the irradiation of a second ion group and the measurement of secondary ions are repeated, and hence analysis accuracy and reproducibility are degraded. Thus, it is preferred that the change be monitored and fed back to the setting conditions of the device so that the change is suppressed.
The ion current value or the cluster size of the second ion group can be directly measured. In this case, a mass spectrum is obtained by irradiating an MCP set in the device with the second ion group. The ion current value is obtained from a peak area value of the mass spectrum, and the cluster size is obtained from the mass and half-value width in that peak. By sampling the ion current value and the cluster size regularly during the irradiation of the ion group for a long period of time through use of the above-mentioned method, changes thereof can be monitored.
Further, the ion current value of the second ion group can also be determined by calculating the ion current value based on a current value of a continuous ion beam before being selected as the second ion group. In this case, first, the sample holding mechanism or another portion in the device is irradiated with the continuous ion beam, and a current value is measured. Next, the ion current value of the ion group is calculated through use of the measured current value and a duty ratio (time width of the second ion group/start time interval of a chopping operation for selecting the second ion group) for selecting the ion group from the continuous ion beam. More preferably, the Faraday cup included in the sample holding mechanism is irradiated with the continuous ion beam, and a current value thereof can be measured. By sampling the ion current value regularly during the irradiation of the second ion group for a long period of time through use of the above-mentioned method, a change thereof can be monitored.
Further, the change in ion current value or cluster size of the second ion group can also be determined from the total amount of secondary ions generated from the sample surface to be irradiated with the second ion group. When the ion current value becomes small, the total amount of secondary ions also decreases. Further, when the cluster size becomes smaller, sputtering efficiency decreases even at the same ion current value, and hence the total amount of secondary ions also decreases. Thus, by measuring, with the mass spectrometer, the total amount of secondary ions obtained for each cycle in which the irradiation of a second ion group and the measurement of secondary ions are repeated during the irradiation of the second ion group for a long period of time, the change in ion current and cluster size can be monitored.
Any one of the ion current value and the cluster size may be monitored, or both of them may be monitored.
The result of monitoring is fed back to the setting conditions of the ion group irradiation device so that the setting conditions are adjusted. The setting conditions may be adjusted regarding an initial value of the ion current value or the cluster size in an initial stage of ion irradiation or the total amount of secondary ions generated from the sample surface to be irradiated with the ion group based on any one of an initial value at the start of irradiation of the second ion group, an average value during irradiation of the second ion group, and a value obtained by monitoring one time before this time of monitoring. Alternatively, the setting conditions may be adjusted based on a set value of the ion current value or the cluster size to be determined by the setting conditions.
There is no particular limit to the setting conditions to be adjusted by feedback. Note that, a change in ion current value or cluster size is mainly caused by a change in pressure of the ion material jetted from the intermittent value. Therefore, examples of the setting condition to be adjusted by feedback include a pressure of an ion material to be supplied to an intermittent valve, a pressure in the vicinity of the intermittent valve, and a time width and an operation time interval of the intermittent valve. Besides those, the operation time interval between the intermittent valve and the chopper, and the time width and operation time interval of the chopper may be adjusted. Further, the distance between the intermittent valve and the ionization unit may be adjusted. Further, voltages to be applied to the intermittent valve, the ionization unit, the chopper, the ion separator, and the like may be adjusted. Further, the number of irradiations of an ion group may be adjusted.
The monitoring of changes in ion current and cluster size, and the adjustment of various setting conditions by the feedback thereof may be performed manually by a measurer or may be performed automatically by a device.
The other configurations are the same as those of the above-mentioned embodiments.
This embodiment has a feature in that two or more second ion groups are formed of three or more ion groups of three or more kinds.
When the sample is irradiated with three kinds of second ion groups, three kinds of different secondary ion mass spectra are obtained. In this case, two or more kinds of mass spectra subjected to difference analysis through use of two kinds of mass spectra are obtained, which enables secondary analysis processing of further subjecting those two mass spectra to difference analysis, with the result that analysis with high accuracy can be performed. In addition, in the case where there are three or more kinds of second ion groups, secondary ion mass spectra do not necessarily need to be obtained from primary ions having masses adjacent to each other. Thus, any combination can be selected, which may omit the processing such as normalization in some cases. Therefore, three or more kinds of second ion groups can be used preferably.
The other configurations are the same as those of the above-mentioned embodiments.
A twenty-first embodiment of the present invention has a feature of including an intermittent valve for supplying an ion material.
The configuration of this embodiment is described with reference to
In an apparatus of this embodiment, as illustrated in
The intermittent valve refers to a valve including an opening and having a function of repeating opening and closing intermittently. The intermittent valve may have a function of not completely closing the opening even in a closed state. Note that, it is preferred that the opening be completely closed in the closed state from the viewpoint of vacuum maintenance in a jetting space.
There are the following kinds of intermittent valves in terms of a valve disc structure: a gate valve, a glove valve, a ball valve, a butterfly valve, a needle valve, and a diaphragm valve. Further, there are the following kinds of intermittent valves in terms of a valve disc drive system: an electromagnetic valve, an electric valve, an air valve, and a hydraulic valve. As the intermittent valve of the present invention, any kind can be used. Note that, the electromagnetic valve is preferably used from the viewpoint of a response speed. Examples of the electromagnetic valve include a poppet type, a spool type, and a slide type in terms of an opening/closing mechanism of a valve seat, and any kind may be used.
An example of a timing chart of a chopper operation according to this embodiment is described with reference to
There is no particular limit to a drive method of an opening and closing operation of the intermittent valve, and any suitable drive method may be selected depending on the kind of the intermittent valve. In the case where the intermittent valve is an electromagnetic valve, the opening and closing operation of the intermittent valve can be performed with satisfactory accuracy by supplying a voltage through use of a waveform generator. Further, a voltage application signal to the intermittent valve can be branched and sent to the chopper as a trigger signal at the same time or times delayed by a predetermined period of time via a delay time generation device. In this case, the jetting operation of the ion material by the intermittent valve and the chopping operation by the chopper can be coordinated with each other with satisfactory accuracy.
The other configurations are the same as those of the first embodiment.
A twenty-second embodiment of the present invention has a feature in that the same sample is irradiated with two or more ion groups.
If the same sample is used, two or more secondary ion mass spectra to be obtained can be compared to each other easily, and hence the accuracy of peak distinction is enhanced.
The other configurations are the same as those of the second embodiment.
A twenty-third embodiment of the present invention has a feature in that the same region is irradiated with two or more ion groups at different times.
This embodiment is described with reference to
Note that, when a region including the same position in the same sample is irradiated with two or more ion groups simultaneously, secondary ions are also generated simultaneously. Therefore, secondary ion spectra obtained from the above-mentioned position become spectra in which two mass spectra overlap each other, and hence the accuracy of peak distinction is degraded. Therefore, in this embodiment, the same region is irradiated with two or more ion groups at different times.
Further, in this embodiment, the time difference between ion groups for irradiation is preferably 10 μsec to 10,000 μsec, more preferably 100 μsec to 1,000 μsec.
The other configurations are the same as those of the second embodiment.
A twenty-fourth embodiment of the present invention has a feature in that a sample is irradiated with two or more ion groups during a certain period of time in the order from ion groups formed of ions having a larger average mass. In this embodiment, the damages to the sample caused during measurement can be reduced by irradiating the sample with ion groups in the order from those formed of ions having a larger average mass.
An example of a timing chart of a chopper operation in the case of using a configuration including a first chopper, a time-of-flight mass separator, and a second chopper in this embodiment is described with reference to
The other configurations are the same as those of the second embodiment.
An twenty-fifth embodiment of the present invention has a feature in that a sample is irradiated with two or more ion groups coaxially.
The coaxial irradiation refers to that a solid angle (hereinafter referred to as “incident angle”) at which an ion group strikes a sample surface is the same between ion groups. The incident angle is determined by conditions such as the solid angle in a direct advancing direction of ions in a primary ion irradiation unit with respect to a sample surface and a voltage applied to primary ions. Note that, even in the case where ion groups of the same kind are incident on a sample in the same condition, the incident angle thereof may vary slightly depending on the charged state of a sample, the fluctuation of a vacuum degree, and the like. Therefore, in the present invention, the difference in incident angle between ion groups being in a range of 0 to 1 degree may be regarded as an error range, and the incident angle may be regarded as the same, that is, coaxial. The generation efficiency of secondary ions from a sample depends on an incident angle. The difference in secondary ion generation efficiency, which is caused by the difference in incident angle dependency between respective ion group irradiations, can be eliminated by rendering the incidence to a sample coaxial. Therefore, the accuracy of comparison analysis of secondary ion mass spectrum can be enhanced by irradiating a sample with two or more ion groups coaxially.
A mass distribution image obtained by the irradiation of an ion group may be distorted depending on an incident angle. The difference in mass distribution image distortion, which is caused by the difference in incident angle between respective ion group irradiations, can be eliminated by rendering incidence to a sample coaxial. Therefore, the accuracy of comparison analysis of a mass distribution image can be enhanced by irradiating a sample with two or more ion groups coaxially.
The other configurations are the same as those of the second embodiment.
A twenty-sixth embodiment of the present invention has a feature in that the number of times of irradiation of two or more ion groups is determined based on ion current values of the ion groups. The ion current value is measured as a value of a current flowing through a target when the target is irradiated with an ion group. The current value is a charge amount per unit time, and hence corresponds to the number of ions with which the sample is irradiated with one specified ion group. When an ion current value of a specified ion group out of multiple ion groups is small, the number of ions with which the sample is irradiated per ion group is small, and hence the number of secondary ions to be generated from the sample also becomes small. Consequently, the intensity of the obtained secondary ion mass spectrum becomes small as a whole and may not be sufficiently compared to mass spectra obtained by the irradiation of the other ion groups in some cases. In this embodiment, the number of irradiations can be set to be larger in advance, for example, with respect to an ion group having a small ion current value. That is, in this embodiment, the difference in spectrum caused by the difference in ion group is reduced, and mass spectra of secondary ions which can be compared to each other are obtained.
Although the relationship between the ion current value and the number of irradiations is not particularly limited, it is preferred that the number of irradiations be determined so that the product of an ion current value and the number of irradiations of each kind of ion groups becomes a difference within one order of magnitude for each ion group.
The ion current value may be obtained by directly measuring a current value of an ion group selected by the first and second choppers or by calculating the ion current value based on a current value of a continuous ion beam before being selected to an ion group.
In the case of directly measuring the current value of the ion group, a micro-channel plate (MCP) is irradiated with the ion group to obtain a mass spectrum, and a peak area value thereof is used.
On the other hand, in the case of calculating the ion current value based on the current value of the continuous ion beam, first, the sample holding mechanism or another portion in the device is irradiated with the continuous ion beam, and a current value thereof is measured. More preferably, the Faraday cup included in the sample holding mechanism is irradiated with the continuous ion beam, and a current value thereof is measured. Next, the ion current value of an ion group is calculated through use of the measured current value and a duty ratio (time width of an ion group/time interval for selecting an ion group) for selecting the ion group from the continuous ion beam.
The ion current value obtained as described above regarding each ion group is fed back to setting conditions for determining the number of irradiations of the ion group irradiation device. The product of the ion current value and the number of irradiations becomes a total charge amount with which the sample is irradiated, and hence the number of irradiations can be determined based on an obtained ion current and setting of the total charge amount.
The measurement and calculation of the ion current, and the determination of the number of irradiations by the feedback of the measurement and calculation may be performed manually by a measurer or may be performed automatically by a device.
The other configurations are the same as those of the second embodiment.
A twenty-seventh embodiment of the present invention has a feature in that two or more ion groups include three or more ion groups in which ions forming the ion groups have different average masses and an atom species or molecule species of the ions forming the ion groups is common between the ion groups.
The three or more ion groups in this embodiment include three or more kinds of ion groups. Note that, in the case where an atom species or molecule species of ions included in the ion groups is common between the ion groups, the kind of each ion group is determined based on the average mass of ions of each ion group. That is, when the average masses of the ion groups are the same, those ion groups are counted as one kind.
When the sample is irradiated with three kinds of ion groups, three different secondary ion mass spectra are obtained. In this case, two or more mass spectra subjected to difference analysis through use of two mass spectra are obtained, which enables secondary analysis processing of further subjecting those two mass spectra to difference analysis, with the result that analysis with high accuracy can be performed. In addition, in the case where there are three or more ion groups, secondary ion mass spectra do not necessarily need to be obtained from primary ions having masses adjacent to each other. Thus, any combination can be selected, which may omit the processing such as normalization in some cases. Therefore, the three or more ion groups can be used preferably.
The other configurations are the same as those of the second embodiment.
An twenty-eighth embodiment of the present invention has a feature in that at least one of two or more ion groups includes cluster ions. When the cluster ions are used, the fragmentation of sample molecules can be suppressed. Therefore, precursor ions can be detected with high sensitivity even with respect to sample molecules having a large mass.
The cluster size range of the cluster ions to be used is not particularly limited and may be determined arbitrarily based on the mass range of target molecules. In general, as the cluster size becomes larger, precursor ions can be detected with more satisfactory sensitivity even with respect to molecules having a large mass.
Note that, the cluster size can be calculated through use of the average mass of ions forming an ion group.
The other configurations are the same as those of the second embodiment.
A twenty-ninth embodiment of the present invention has an feature in that an ion material contains any one of a gas, a liquid, and a mixture of a gas and a liquid at normal temperature and normal pressure. In the present invention, the kind of the ion material is not particularly limited. However, cluster ions having a larger cluster size can be generated easily by using a gas or a non-metal liquid as the ion material rather than by using a liquid metal. As the cluster size increases, precursor ions can be detected with high sensitivity even with respect to molecules having a large mass. Therefore, it is preferred that the ion material contain any one of a substance that is a gas, a substance that is a liquid, and a mixture of a substance that is a gas and a substance that is a liquid at normal temperature and normal pressure.
Examples of the gas at normal temperature and normal pressure include rare gases such as argon and xenon. Note that, the present invention is not limited thereto.
Examples of the liquid at normal temperature and normal pressure include water, an acid, an alkali, and an organic solvent such as an alcohol. Note that, the present invention is not limited thereto.
The other configurations are the same as those of the second embodiment.
A thirtieth embodiment of the present invention has a feature in that at least one of the two or more ion groups contains at least one kind of molecule of water, an acid, and an alcohol. In the present invention, a constituent atom species or molecule species of ions forming two or more ion groups is not particularly limited. However, when a sample is irradiated with primary ions containing at least one kind of molecule of water, an acid, and an alcohol, due to proton donor ability of molecules forming the primary ions, molecules having a proton affinity such as biological molecules can be accelerated to generate proton adduct ions. As a result, the detection sensitivity of precursor ions of the molecules is enhanced. Therefore, it is preferred that at least one of the two or more ion groups contain at least one kind of molecule of water, an acid, and an alcohol.
There is no particular limit to ions containing water, and preferred examples thereof include [(H2O)n]+ (n=1 to 100,000) and [(H2O)n+mH]m+ (n=1 to 100,000, m=1 to 100,000).
An example using the following two ion groups is described below: an ion group in which water molecules are formed of 1,000±20 water cluster ions ([(H2O)1000±20]+); and an ion group in which water molecules are formed of 10,000±200 water cluster ions ([(H2O)10000±200]+). Note that, [(H2O)1000±20]+ refers to ions obtained as a result of an error of ±20 in selecting an ion group although an average of the numbers of water molecules included in ions is 1,000. Similarly, [(H2O)10000±200]+ refers to ions obtained as a result of an error of ±200 in selecting an ion group although an average of the numbers of water molecules included in ions is 10,000.
Water cluster ions can be obtained by heating water serving as an ion material with the ion material supply unit, spraying the heated water in a vacuum, subjecting the neutral water cluster, and ionizing the formed neutral water cluster by electron impact ionization. A part of an aggregate of ionized ions having multiple cluster sizes is selected as an ion group with the first chopper. The ion group is subjected to mass separation with the time-of-flight mass separator. After the elapse of a specified time period ΔT1 from the chopping operation by the first chopper, the second chopper performs a chopping operation to select an ion group formed of [(H2O)10000±200]+. A sample containing biological molecules is irradiated with the selected ion group formed of [(H2O)10000±200]+, and a secondary ion mass is analyzed. Assuming that one cycle includes the chopping operation by the first chopper to the secondary ion mass analysis in the foregoing description, the sample is irradiated with an ion group formed of [(H2O)1000±20]+ in the same way as in the first cycle by changing the period of time of the chopping operation by the first chopper to ΔT2 (ΔT2<ΔT1) in the subsequent cycle, and a secondary ion mass is analyzed. A precursor ion peak of biological molecules is obtained with satisfactory sensitivity in the two secondary ion mass spectra obtained as described above. Therefore, the distinction of precursor ions and the identification of biological molecule species are performed easily by comparison analysis processing. Note that, the present invention is not limited to the above-mentioned example.
The kind of the acid is not particularly limited, and preferred examples thereof include formic acid, acetic acid, and trifluoroacetic acid.
The kind of the alcohol is not particularly limited, and preferred examples thereof include methanol, ethanol, and isopropyl alcohol. There is no particular limit to the number and ratio of water, acid, and alcohol molecules included in ions of one irradiation. Note that, as the number of the water, acid, and alcohol molecules becomes larger, a protonation ratio is enhanced in some cases.
The other configurations are the same as those of the second embodiment.
A thirty-first embodiment of the present invention has a feature in that at least one of two or more ion groups includes rare gas molecules. In the present invention, a constituent atom species or molecule species of ions forming the two or more ion groups is not particularly limited. However, when the sample is irradiated with primary ions including rare gas molecules, the contamination of the sample surface involved in the irradiation of primary ions can be prevented because the reactivity of the rare gas molecules is low. Therefore, it is preferred that at least one of the two or more ion groups include rare gas molecules. Although there is no particular limit to the kind of the rare gas molecules, argon or xenon can be preferably used from the viewpoint of a mass and cost. The other configurations are the same as those of the second embodiment.
A thirty-second embodiment of the present invention has a feature in that ions forming two or more ion groups include an atom species or molecule species which is the same between the ion groups. In this case, even when a sample is irradiated with ions having different average masses, the difference in reactivity between the primary ions and the sample molecules can be reduced further. In addition, in this case, signals derived from primary ions are more similar to each other, and hence the difference between multiple secondary ion mass spectra can be analyzed with satisfactory accuracy.
The atom species or molecule species forming the two or more ion groups is not limited. As ions (i) and (ii) forming two ion groups, there is preferably given, for example: (i) [(H2O)n(CH3OH)p]+ and (ii) [(H2O)m(CH3OH)q]+ (n=1 to 100,000, m=1 to 100,000, p=1 to 100,000, q=1 to 100,000, provided that at least one of the following is satisfied: n and m are not equal to each other and p and q are not equal to each other); or (i) [(H2O)n(HCOOH)p]+ and (ii) [(H2O)m(CH3OH)q(HCOOH)r]+ (n=1 to 100,000, m=1 to 100,000, p=1 to 100,000, q=1 to 100,000, r=1 to 100,000).
The other configurations are the same as those of the second embodiment.
A thirty-third embodiment of the present invention has a feature in that ions forming two or more ion groups have a configuration ratio of an atom species or molecule species, which is the same between the ion groups. In this case, even when a sample is irradiated with ions having different average masses, the difference in reactivity between primary ions and the sample molecules can be reduced most. Further, when an atom species or molecule species forming primary ions is the same, signals derived from the primary ions included in secondary ions are most similar to each other, and hence the difference between multiple secondary ion mass spectra can be analyzed with satisfactory accuracy.
As a result, even in the case where a sample is irradiated with two or more ion groups having different average masses, the generation of secondary ions of a specific kind or amount can be most suppressed.
Note that, in calculation of a configuration ratio of an atom species or molecule species in this embodiment, the addition or removal of atoms or molecules occur depending on the kind of ionization, and hence a variation of ±1 can be ignored regarding each number of atoms or molecules. For example, in the case of a proton adduct ion containing one water molecule [H2O]H+ and a molecular ion containing 1,000 water molecules [(H2O)1000+], only the former contains one hydrogen besides the water molecule. However, the configuration ratios of an atom species and a molecule species may be set to be the same (both the atom species configuration ratios are 2:1 (hydrogen atom:oxygen atom), and both the molecule species configuration ratios are 100% of water molecule).
The atom species or molecule species forming the two or more ion groups is not limited. As ions (i) and (ii) forming two ion groups, there is preferably given, for example: (i) [(H2O)]n+ and (ii) [(H2O)m]+ (n=1 to 100,000, m=1 to 100,000, provided that n and m are not equal to each other); (i) [(H2O)n(CH3OH)p]+ and (ii) [(H2O)m(CH3OH)q]+ (n=1 to 100,000, m=1 to 100,000, p=1 to 100,000, and q=1 to 100,000, provided that n and m are not equal to each other, p and q are not equal to each other, and a ratio between n and p is equal to a ratio between m and q); or (i) [(H2O)n(HCOOH)m]+ and (ii) [(H2O)p(HCOOH)q]+ (n=1 to 100,000, m=1 to 100,000, p=1 to 100,000, and q=1 to 100,000, provided that n and p are not equal to each other, m and q are not equal to each other, and an n/m ratio is equal to a p/r ratio).
The other configurations are the same as those of the second embodiment.
A thirty-fourth embodiment of the present invention has a feature in that, as the mass spectrometer for measuring secondary ions, a time-of-flight mass spectrometer is used.
The time-of-flight mass spectrometer guides all the secondary ions generated from the sample to an extraction electrode and accelerates the secondary ions at an acceleration voltage V, and thereafter allows the secondary ions to fly through a free space having the flight-path length L to reach a detector. The secondary ions are separated for each mass-to-charge ratio, and hence the mass “m” of each secondary ion can be determined based on Expression (1) by measuring the arrival time “t” of the ions to the detector.
The time-of-flight mass spectrometer has high mass resolution. In addition, the time-of-flight mass spectrometer has high detection sensitivity due to excellent transmittance of secondary ions. Further, a parameter to be controlled for detecting secondary ions is only time, and hence the convenience of control is high. As described above, secondary ion mass analysis with high mass resolution and high sensitivity can be performed easily, and hence the above-mentioned device can be used preferably.
The secondary ion measurement by the time-of-flight mass spectrometer can be controlled easily in coordination with a second chopper. As the time for starting measurement of secondary ions, the chopping operation start time of the second chopper may be used or the time delayed by a predetermined time period from the chopping operation start time of the second chopper may be used. In the case of using the time delayed by the predetermined time period, temporal axes of secondary ion mass spectra obtained by the irradiation of respective ion groups can also be substantially aligned with each other by changing the delayed time in accordance with an ion group with which a sample is irradiated. Further, as the time for finishing measurement of secondary ions, the time delayed by a predetermined time period from the time for starting measurement of secondary ions may be used. Alternatively, assuming that one cycle includes operations conducted in the following order in a time series: chopping by the first chopper, chopping by the second chopper, and measurement of secondary ions by the time-of-flight mass spectrometer, as the time for finishing measurement of secondary ions, the time for starting a chopping operation by the first or second chopper in the subsequent cycle may be used. In the time-of-flight mass spectrometer, measurement time corresponds to a measurement mass range, and hence the measurement time may be determined based on a mass range to be measured.
In the case of using the time-of-flight mass spectrometer, a sample for mass calibration is measured for each ion group with which a sample to be analyzed is irradiated before the sample is measured, and temporal axes of time-of-flight (corresponding to an axis of a mass-to-charge ratio) may be calibrated in each case. Consequently, the mass accuracy in obtained secondary ion mass spectra is enhanced, and the comparison accuracy of different secondary ion mass spectra is enhanced.
The other configurations are the same as those of the second embodiment.
In a thirty-fifth embodiment of the present invention, the mass spectrometer for measuring secondary ions includes a detector having a two-dimensional ion detection function of detecting secondary ions generated from the sample surface while keeping a positional relationship at a secondary ion generation position.
When the mass spectrometer including the detector having the two-dimensional ion detection function is used, the generation position of secondary ions on the sample surface can be recorded, and hence it is not necessary to scan primary ions. Therefore, a target region on the sample can be irradiated with primary ions simultaneously, and secondary ions at each position in the target region can be detected collectively. Consequently, compared to the case of scanning primary ions, measurement can be completed within a short period of time.
The mass spectrometer of this embodiment may include a projection adjusting electrode for adjusting a projection magnification besides an extraction electrode, a mass separation portion, and the above-mentioned detector. The projection adjusting electrode has a function of enlarging or reducing a spatial distribution of secondary ions on a two-dimensional plane perpendicular to the traveling direction of secondary ions directed to the detector.
Secondary ions generated from the sample surface due to the irradiation of the ion group are extracted by the extraction electrode supplied with a voltage of several to several 10 kV. Next, the extracted secondary ions are enlarged or reduced by any projection magnification with the projection adjusting electrode and introduced into the mass separation portion. Then, the introduced secondary ions are separated based on a mass-to-charge ratio and further enlarged or reduced as needed. In the above-mentioned process, the relative positional relationship of the secondary ions on the sample surface is kept. The separated secondary ions are successively detected with the detector, and the mass information and two-dimensional position information are recorded.
Although the mass separation system in the mass spectrometer in this embodiment is not particularly limited, for example, the detection time (corresponding to the mass of secondary ions) and detection position of secondary ions can be recorded simultaneously through use of a time-of-flight mass separation system.
There is no particular limit to the kind of the detector having the two-dimensional ion detection function, and a detector having any configuration can be used as long as the detector can detect a time and a position at which ions are detected. For example, any one of a combination of a micro-channel plate (MCP) and a two-dimensional electron position detector (for example, a delay line detector), a combination of the MCP and a fluorescent plate, a combination of the MCP and a charge-coupled device (CCD) two-dimensional detector, and a detector in which minute MCPs are arranged two-dimensionally can be used.
When secondary ions are measured through use of the mass spectrometer in this embodiment, a sample is irradiated with an ion group by a projection type, and secondary ions generated from a whole or a part of an irradiation region are measured. The irradiation position and area of the ion group can be determined arbitrarily based on the ion current amount, incident angle, distance between the sample surface and the ion irradiation unit, and the like through use of the primary ion irradiation device. The area and projection magnification of a secondary ion measurement target region can be determined arbitrarily based on the distance between the extraction electrode and the sample, voltage applied to the extraction electrode, voltage applied to the projection adjusting electrode, and the like.
When secondary ions are measured through use of the mass spectrometer in this embodiment, secondary ions may be measured continuously or discretely for one irradiation of an ion group. In the case where the secondary ions are measured discretely, a mass distribution image of target molecules can be obtained at a high speed by controlling a measurement timing in accordance with the mass information of the target molecules.
The other configurations are the same as those of the second embodiment.
In a thirty-sixth embodiment of the present invention, a change in ion current value or cluster size of the ion group with which the sample is irradiated is monitored, and the monitored change is fed back to setting conditions of the device so that the change is suppressed.
In the case where the selection and irradiation of an ion group are performed for a long period of time, a current value and a cluster size of the ion group may change even when the setting conditions of the device are the same during the selection and the irradiation. In this case, measurement results vary for each cycle in which the irradiation of an ion group and the measurement of secondary ions are repeated, and hence analysis accuracy and reproducibility are degraded. Thus, it is preferred that the change be monitored and fed back to the setting conditions of the device so that the change is suppressed.
The ion current value or the cluster size of the ion group can be directly measured. In this case, a mass spectrum is obtained by irradiating an MCP set in the device with the ion group. The ion current value is obtained from a peak area value of the mass spectrum, and the cluster size is obtained from the mass and half-value width in that peak. By sampling the ion current value and the cluster size regularly during the irradiation of the ion group for a long period of time through use of the above-mentioned method, changes thereof can be monitored.
Further, the ion current value of the ion group can also be determined by calculating the ion current value based on a current value of a continuous ion beam before being selected as the ion group. In this case, first, the sample holding mechanism or another portion in the device is irradiated with the continuous ion beam, and a current value is measured. More preferably, the Faraday cup included in the sample holding mechanism is irradiated with the continuous ion beam, and a current value thereof is measured. Next, the ion current value of the ion group is calculated through use of the measured current value and a duty ratio (time width of the ion group/start time interval of a chopping operation for selecting the ion group) for selecting the ion group from the continuous ion beam. By sampling the ion current value regularly during the irradiation of the ion group for a long period of time through use of the above-mentioned method, a change thereof can be monitored.
Further, the change in ion current value or cluster size of the ion group can also be determined from the total amount of secondary ions generated from the sample surface irradiated with the ion group. When the ion current value becomes small, the total amount of secondary ions also decreases. Further, when the cluster size becomes smaller, sputtering efficiency decreases even at the same ion current value, and hence the total amount of secondary ions also decreases. Thus, by measuring, with the mass spectrometer, the total amount of secondary ions obtained for each cycle in which the irradiation of an ion group and the measurement of secondary ions are repeated during the irradiation of the ion group for a long period of time, the change in ion current and cluster size can be monitored.
Any one of the ion current value and the cluster size may be monitored, or both of them may be monitored.
The result of monitoring is fed back to the setting conditions of the ion group irradiation device so that the setting conditions are adjusted. The setting conditions may be adjusted regarding an initial value of the ion current value or the cluster size in an initial stage of ion irradiation or the total amount of secondary ions generated from the sample surface irradiated with the ion group based on any one of an initial value at the start of irradiation of the ion group, an average value during irradiation of the ion group, and a value obtained by monitoring one time before this time of monitoring. Alternatively, the setting conditions may be adjusted based on a set value of the ion current value or the cluster size to be determined by the setting conditions.
There is no particular limit to the setting conditions to be adjusted by feedback. Note that, a change in ion current value or cluster size is mainly caused by a change in pressure of the ion material jetted from the intermittent valve. Therefore, examples of the setting condition to be adjusted by feedback include a pressure of an ion material to be supplied to an intermittent valve, a pressure in the vicinity of the intermittent valve, and a time width and an operation time interval of the intermittent valve. Besides those, the operation time interval between the intermittent valve and the chopper, and the time width and operation time interval of the chopper may be adjusted. Further, the distance between the intermittent valve and the ionization unit may be adjusted. Further, voltages to be applied to the intermittent valve, the ionization unit, the chopper, the ion separator, and the like may be adjusted. Further, the number of irradiations of an ion group may be adjusted.
The monitoring of changes in ion current and cluster size, and the adjustment of various setting conditions by the feedback thereof may be performed manually by a measurer or may be performed automatically by a device.
The other configurations are the same as those of the second embodiment.
In a thirty-seventh embodiment of the present invention, there is provided a secondary ion mass spectrometry including comparing secondary ion mass spectra for each ion group for irradiation, and obtaining a mass spectrum or a mass distribution image based on the difference thereof, through use of the secondary ion mass spectrometer of the present invention.
In a thirty-eighth embodiment of the present invention, there is provided a secondary ion mass spectrometer for irradiating a sample with an ion group. The secondary ion mass spectrometer includes an ion source for generating ions, an ion group selecting unit configured to select two or more ion groups from the ions released from the ion source, and a primary ion irradiation unit configured to irradiate the sample with the two or more ion groups. Further, an atom species or molecule species of the ions forming the two or more ion groups is common between the ion groups, and the ion group selecting unit includes a first chopper positioned on the ion source side, a second chopper, and an ion separator disposed between the first and second choppers. The ion source includes an intermittent valve. The intermittent valve performs a jetting operation of intermittently jetting an ion material. The first and second choppers each perform a chopping operation of selecting an ion group by passing and blocking the ions in a traveling direction through opening and closing. The secondary ion mass spectrometer is operated in a first operation mode in which at least one of the first and second choppers performs the chopping operation multiple times in coordination with one jetting operation by the intermittent valve, in a second operation mode in which the second chopper performs one chopping operation in coordination with one chopping operation by the first chopper, and in a specified cycle in which the chopping operation by the first chopper and the chopping operation by the second chopper are repeated multiple times, there are multiple differences between an opening time of the first chopper and an opening time of the second chopper, and in a third operation mode in which the second chopper performs the chopping operation multiple times in coordination with one chopping operation by the first chopper. The secondary ion mass spectrometer is operated in a combination of at least two of the first, second, and third operation modes.
The secondary ion mass spectrometer of this embodiment may be operated in a combination of the first and second operation modes. The secondary ion mass spectrometer of this embodiment may also be operated in a combination of the first and third operation modes. The secondary ion mass spectrometer of this embodiment may also be operated in a combination of the second and third operation modes. Further, the secondary ion mass spectrometer of this embodiment may also be operated in a combination of the first, second, and third operation modes. Each operation of the intermittent valve, the first chopper, and the second chopper may coordinated with each other in accordance with the above-mentioned combination. Note that, the operation of the mass spectrometer may be coordinated with any one of the operations of the intermittent valve, the first chopper, and the second chopper.
The other configurations are the same as those of the second, third, fourth and fifth embodiments.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-131783 | Jun 2013 | JP | national |
| 2013-131874 | Jun 2013 | JP | national |
This application is a continuation-in-part of U.S. application Ser. No. 14/306,485, filed Jun. 17, 2014, which claims the benefit of Japanese Patent Application No. 2013-131874, filed Jun. 24, 2013, and is a continuation-in-part of U.S. application Ser. No. 14/296,973, filed Jun. 5, 2014, which claims the benefit of Japanese Patent Application No. 2013-131783, filed Jun. 24, 2013. The contents of all of these prior applications are hereby incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14296973 | Jun 2014 | US |
| Child | 14734692 | US | |
| Parent | 14306485 | Jun 2014 | US |
| Child | 14296973 | US |
