CN207396353U - A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample - Google Patents
A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample Download PDFInfo
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Abstract
The utility model discloses the quantitative analysis devices that a kind of spectrum combines element in mass spectrographic unknown sample.The present apparatus combines the quantitative analysis structure and method of a kind of two level extraction field flight time mass spectrum (TOF) using laser induced breakdown spectroscopy.Realization high detection sensitivity, the quantitative analysis device that real-time, quick, high-precision, non-contact type, multielement detect simultaneously and sample need not pre-process.Dual-wavelength laser wherein in the device convenient for ionizing light fragment and molecular cluster again, improves mass signal stability, enhances Laser Plasma Emission Spectrum signal；Two level draws field in the device, convenient for improving TOF mass resolutions and optimization signal；Spectral collection system in the device can improve collection plasma emissioning light and be coupled to the ability of optical fiber, and can fold light path, instrument integration, miniaturization are very advantageous in, convenient for instrument commercialization.
Description
Technical field
The utility model is related to detection technique fields more particularly to a kind of spectrum to combine element in mass spectrographic unknown sample
Quantitative analysis device.
Background technology
1960 American scientist Maiman utility models first ruby laser, then scientist's utility model
The method of plasma generation with laser, 1962, in the tenth international spectroscopy collection of thesis, Fred Brech were proposed at first
The spectrochemistry method for generating plasma is induced with ruby maser, before this is also laser induced breakdown spectroscopy
Body.Scientist in 1963 has begun to carry out material surface analysis using laser ablation plasma, but due to laser at that time with
And the limitation of spectra collection system causes spectral signal to collect hardly possible, of poor quality, scientist once lost interest to this method.However
With the development of laser technology, the generation of high power pulse laser and the upgrading of spectral detector so that laser ablation etc. from
New upsurge has been shone in daughter again.After nineteen eighty-three, laser induced breakdown spectroscopy starts with abbreviated form " LIBS "
(Laser-Induced Breakdown Spectroscopy) is constantly appeared in relevant document, over nearly more than 30 years,
LIBS measurement technologies are all widely used in industry-by-industry field, such as environmental monitoring, drugs monitoring, food safety monitoring, work
Industry production monitoring, nuclear fusion device inline diagnosis, cultural heritage identification, Gemstone Identification, dangerous material remote probe etc..Induced with laser
Breakdown spectral technology (LIBS) is a kind of based on the atomic emission spectrum technology that high energy pulse laser ionization is used to be analyzed sample
(AES), because it is a kind of pure optical technology, optical system can be combined and carry out remote, high sensitivity detection.Compared to tradition
AES technologies, LIBS technologies have sample without pretreatment, sampling less, micro-zone analysis, multielement detect simultaneously, analyze speed
The advantages that fast.
The LIBS researchs of early stage are concentrated mainly in the qualitative analyses such as sample on-line monitoring, long-range detection, sample classification,
Castle in 1997 etc. uses LIBS technologies as a kind of new quantitative analysis tech, studies its detection limit, precision, accuracy
Etc., and compared with other existing quantitative analysis tech, find laser induced breakdown spectroscopy analyze speed,
Multielement detects, detects limit etc. with advantage simultaneously.Afterwards, both at home and abroad many LIBS seminar by its research emphasis
It focuses on LIBS quantitative analysis tech.The difficult point of LIBS technology quantitative analysis samples is broadly divided into following side with challenge
Face:(1) plasma processes induced by laser factor is generated：Including laser-material interaction, laser-plasma phase interaction
With, plasma-material interaction process；(2) plasma itself factor：Including the movement of particle, excitation, from
Change, radiate and interact with environmental gas；(3) plasma emissioning light collects factor：As self-absorption, optical coupling, optical transport,
Optical detection etc.；(4) parameter factor：Such as the later stage calculates Einstein's emission ratio used, the error of partition function parameter.Its
In preceding 3 major class problem correspond to 3 most basic hypothesis in LIBS quantitative analysis process：Chemical Measurement ablation
(Stoichiometric ablation)；Local thermodynamical equilibrium (Local Thermodynamic Equilidrium,
LTE)；Optically thin (optical thin).
For the above factor for restricting LIBS quantitative analyses, scientist is analyzed by experimental study and theoretical modeling, and is made
Mathematically quantitative analysis process error that may be present is corrected, to improve quantitative precision and precision.It is wherein right
In interaction factor, since the spectrum experimentally collected is emitted by laser plasma, cause last quantitative analysis
As a result what is represented is the information of laser plasma rather than sample information in itself, this is just it needs to be ensured that ablation generated etc.
Gas ions information can represent material self-information i.e. Chemical Measurement ablation (Stoichiometric ablation, the U.S. primary
Ke Li National Laboratories Chan and Russo is pointed out in the research report of 1991, as laser power ＞ 109W/cm2When, substantially
It may insure Chemical Measurement ablation.According to its viewpoint, laser-material interaction can be described as 2 models:Evaporation mold
Type, ablating model, usually as laser power ＜ 106W/cm2When happens is that melt, evaporation and desorption process, such as μm swash
Light and Long Pulse LASER and material interact, which under normal circumstances, satisfies since lattice transfers energy by thermal diffusion
High element is easier to be enriched under gas phase state with vapour pressure, causes non-stoichiometric ablation；And as laser power ＞
109W/cm2When, occur phase blast process, Electron absorption energy is quick and lattice relaxation, and lattice is by heat transfer into material
Transfer energy in portion so that interior layer temperature moment reaches boiling point, and formation high steam outwards expands, and mutually explosion formation etc. occurs
Gas ions, the element and material itself in the plasma are identical, that is, Chemical Measurement ablation occurs.
For plasma factor itself, since laser plasma body life time (μm) is considerably longer than the laser duration
(ns), this just illustrates, laser plasma is not a simple photoexcitation process, it is therefore desirable to which plasma is in itself
Temporal-spatial evolution is studied, and is understood in it in physical mechanism, is targetedly corrected, improve its quantitative analysis ability.Wait
The processes such as in gas ions evolutionary process, the particle of plasma can collide, excite, ionization and radiation, it is entire etc. to understand
Ion evolutionary process can be radiated by Maxwell's function, Boltzmann's function, Saha's equation and Planck blackbody and retouched respectively
Each process more than stating.Assume initially that plasma is in local thermodynamical equilibrium process (Local Thermodynamic
Equilibrium, LTE), then the importance of the collision process between particle will be prior to particle radiation, therefore in plasma
Portion's electron density needs to meet criterion：ne≥1.6×1012T(ΔE)3, to ensure enough collisions.In addition Bohr can be used
Hereby graceful Slope Method widens calculating etc. with Saha-Boltzmann Slope Method calculating plasma excitation temperature and using Stark
Gas ions electron density, to be used for quantitative analysis.
The self-absorption of light inevitably to occur during plasma emission spectroscopy is collected, can generally use trace
The spectral line that the upper energy level of secondary element is higher carries out internal calibrations to other elements, to reduce the influence of self-absorption；In data analysis
In for reduce self-absorption influence, can also be by avoiding being analyzed using resonance line.In addition growth curve side can be used
Method (Curve Of Growth) is corrected self-absorption.In addition another influences the parameter of spectral collection for optical system
(such as detector is imitated for collection efficiency (as collected optical system, optical fiber transmission, spectrometer grating) and the detection efficient of optical instrument
Rate, booster efficiency, response efficiency of characteristic wavelength etc.), therefore each spectral measurement is all actual physical data and system
The convolution of response.It can be corrected using standard sources or can be in the case where light path is constant in experiment
Know and carry out calculating derivation in the case of optical instrument parameter.
Flight time mass spectrum (Time-of-Flight Mass Spectrometry, TOF-MS) analysis is to utilize kinetic energy phase
With and ions different matter-He Bi moves in steady electric field, by different principles the time required to constant distance to substance into
Point or a kind of mass spectrometric analysis method for being measured of structure.Using the flight time of ion as criterion carry out quality analysis by
Stephnsen nineteen forty-six propose, and the sixties in last century TOF-MS be just used widely.TOF-MS analytical technologies
The advantages of be theoretically there is no mass range limitation to detection object, and all ions for reaching detector can be at same
Mass spectrogram is shown, highly shortened analysis time；Followed by its response speed is exceedingly fast, by change its accelerating field come
Change its kinetic energy, so as to change the flight time of ion；Furthermore by the way that suitable microchannel plate (MCP) coupled ion is selected to catch
Storage sets accelerating field to increase the shock dynamics of ion before detector, generates more electronics, then carries out snowslide electricity
From to improve the detection limit of TOF-MS.Initial ion source is realized using electron bombardment method, and high energy electron is generated by electron gun
Ionized sample makes it be decomposed into ion, then enters movement area by drawing field.Finally, with the development of laser technology, swashed with pulse
Light generates ion source with material interaction and is widely used, if laser desorption is attached (LD), resonance laser ionization (RI),
Substance assistant laser desorpted (MALDI), laser breakdown (LB) and laser ablation (LA) etc..
Laser ablation flight time mass spectrum (LA-TOFMS) is a kind of analysis means to grow up in recent years, this method
Have many advantages, such as spectrogram interference less, sample without pretreatment, detection speed it is fast, can multielement detect simultaneously.It is cold in plasma
But in expansion process, molecular cluster on the one hand can be formed by collision loss energy, on the other hand, due to there is condensation in environment
Core, plasma can form big nano particle.In addition the temperature gradient of plasma temperature and sample surfaces meeting heating material,
Make material melts or evaporation.Above-mentioned dark-state substance, can not spectrally detect, be the key that influence LIBS quantitative techniques because
Element.Therefore with reference to two methods, by emission spectrum, can analyze analyzed sample be excited plasma characteristic parameter such as
Plasma exciatiaon temperature, plasma electron density, ion concentration of different plant species etc. in plasma, and then using obtaining
The anti-composition information for pushing away analyzed sample of emission spectrum signal；Laser ablation Plasma-Mass Spectroscopy draws field handle by a two level
The particle of laser ablation introduces time of-flight mass spectrometer, passes through the anti-composition information for pushing away sample of mass signal obtained by analysis.Hair
The particle information for being excited and being ionized can effectively be analyzed by penetrating spectrum, but cannot detect that laser ablation material produces
Raw nano-particle, molecular cluster, dark-state species, this can increase the error of LIBS quantitative analyses.However flight time mass spectrum is but
It is analysis cluster, the most effective instrument of nano-particle, more accurate quantification point can be carried out to unknown sample with reference to two methods
Analysis.Further, since spectral signature peak is more, determining the ownership of each spectral line becomes a bottleneck of limitation quantitative analysis speed,
LA-TOFMS can help laser induced breakdown spectroscopy quickly to determine the element in material, and the ownership for being characterized peak provides
It helps, can greatly save the time needed for analysis.
Utility model content
The purpose of this utility model is to provide a kind of quantitative analysis device of spectrum with reference to element in mass spectrographic unknown sample.
A kind of spectrum provided by the utility model combines the quantitative analysis device of element in mass spectrographic unknown sample, automatic to adjust
Burnt module connects stepper motor by serial ports, passes through bnc interface connecting laser；Laser passes through bnc interface and timing control
Module connects；The laser that laser is sent is via the laser mirror with incident laser direction placement at 45 °, by swashing with incidence
Condenser lens, vacuum chamber form and the three-dimensional automatic sample sample platform for being placed on condenser lens focal point of light direction placement in 90 °
On sample interaction, formed laser plasma plume brightness；Ablation is triggered on second tunnel and ionization laser enters with the first via
Laser angle in 90 ° is penetrated to interact with plasma plume brightness；Time-sequence control module passes through bnc interface and flight time mass spectrum
Instrument, spectrometer connection；Time of-flight mass spectrometer and extraction field ionization source pass through high pressure port secondary particle and draw field connection；Laser etc.
Ion body feathers brightness emits light and is reflected through emission spectrum collection system by transmitting optically coupling in optical fiber by plane mirror；Optical fiber passes through
SMA905 interfaces will emit optical transport into spectrometer；Dark-state, cluster and the nano-particle warp that laser plasma plume brightness is sent
Field is drawn by secondary particle to enter in flight time mass spectrum；Spectrometer is collected and is coupled to and is centrally disposed perforate non-spectral instrument and leads to
Cross plane mirror, emission spectrum collection system, be placed on focal point optical fiber collect laser plasma plume brightness emission spectrum；Fly
Row time mass spectrum instrument stores analysis module with signal by USB interface with spectrometer and is connected, and signal storage analysis module is according to mould
Type analyzes the spectrum collected with mass spectrum, obtains the elemental composition information of unknown sample.Need specified otherwise is certainly
Detector in dynamic focusing module needs to be fixed in identical platform with condenser lens, to ensure the accuracy of automatic focusing；It is flat
The tandem that face mirror, emission spectrum collection system, optical fiber are placed is immutable.
Preferably, the ablative laser ablation of line focus lens focus is placed on the sample at condenser lens focal position
Form laser plasma；With the ionization laser or resonance laser and laser plasma phase interaction of ablative laser incidence in 90 °
With enhancing plasma spectrometry transmitting；The first order draws field, the second level draws field and connects the flight time respectively by high pressure port
Mass spectrograph and two high voltage power supplies for drawing field ionization source；Electrostatic einzel lens connect time of-flight mass spectrometer by high pressure port and draw
Go out another high-voltage power supply of field ionization source；Most particle is introduced into time of-flight mass spectrometer at last.The position of above-mentioned various pieces must
It must be defined as two level extraction field to be placed on after level-one extraction field, electrostatic einzel lens are placed on after two level extraction field, the flight time
Mass spectrograph collects the particle by electrostatic einzel lens.
Preferably, laser plasma transmitting light is reflected into convex lens, the light that convex lens will be collected into through plane mirror
It is placed on the concavees lens before concave lens focus and is then coupled to the folding for being placed on the optical system that convex lens is formed with concavees lens
In optical fiber at complex focus position.Specified otherwise be plane mirror, convex lens, concavees lens, optical fiber placement order can not
To change.
Advantageous effect：The utility model combination laser induced breakdown spectroscopy realizes high visit with ionization time of flight
Survey sensitivity, the quantitative analysis dress that real-time, quick, high-precision, non-contact type, multielement detect simultaneously and sample need not pre-process
It puts.
Description of the drawings
Fig. 1 is the general structure schematic diagram (positive front upper place visual angle) of the utility model.
Fig. 2 is that the secondary particle of the utility model draws field structure schematic diagram.
Fig. 3 is the utility model spectral collection system structure diagram.
Accessory identification：1st, automatic focusing module；2nd, laser；3rd, laser mirror；4th, laser focusing lens；5th, high-precision
Guide rail；6th, the first stepper motor；7th, vacuum chamber form；8th, three-dimensional automatic sample sample platform；9th, laser plasma plume brightness；10th, two
Grade particle draws field；11st, time of-flight mass spectrometer；12nd, time of-flight mass spectrometer and extraction field ionization source；13rd, quantitative analysis instrument sample
Product room；14th, plane mirror；15th, emission spectrum collection system；16th, optical fiber；17th, spectrometer；18th, signal storage analysis module； 19、
Time-sequence control module；20th, ablation and ionization laser beam；21st, laser measurement module is inputted；22nd, the second stepper motor；23rd, it is tested
Sample；24th, ablative laser；25th, laser or resonance laser are ionized；26th, the first order draws field；27th, field is drawn in the second level；28th, it is quiet
Electric simple lens；29th, high pressure port；30th, particle flight area；31st, laser plasma；32nd, plane mirror；33 convex lenses；
34th, concavees lens；35th, concave lens focus；36th, compound lens focus；37th, optical fiber；38th, simple lens system；39th, optical fiber-slit coupling
Collaboration is united.
Specific embodiment
The technical issues of to solve the utility model, the technical solution used and the technique effect reached are clearer,
The utility model is described in further detail with reference to the accompanying drawings and examples.It is it is understood that described herein
Specific embodiment is used only for explaining the utility model rather than the restriction to the utility model.It also should be noted that it is
Convenient for description, part relevant with the utility model rather than full content are illustrated only in attached drawing.
Fig. 1 is refer to, Fig. 1 is the general structure schematic diagram (positive front upper place visual angle) of the utility model.
Automatic focusing module 1 connects stepper motor 6 by serial ports, passes through bnc interface connecting laser 2；Laser 2 passes through
Bnc interface is connected with time-sequence control module 19；The laser that laser 2 is sent is via sharp with incident laser direction placement at 45 °
Light reflection mirror 3, the condenser lens 4 by with incident laser direction placement in 90 °, vacuum chamber form 7 are saturating with being placed on focusing
Sample interaction in the three-dimensional automatic sample sample platform 8 of 4 focal point of mirror, forms laser plasma plume brightness 9；It touches on the second tunnel
Fever erosion and ionization laser 20 interact with first via incident laser angle in 90 ° with plasma plume brightness 9；Timing control mould
Block 19 is connected by bnc interface with time of-flight mass spectrometer 11, spectrometer 17；Time of-flight mass spectrometer and extraction field ionization source 12
Field 10 is drawn by high pressure port secondary particle to connect；Laser plasma plume brightness 9 emits light and is reflected through hair by plane mirror 14
Penetrating spectral collection system 15 will emit optically coupling in optical fiber 16；Optical fiber 16 will emit optical transport to light by SMA905 interfaces
In spectrometer 17；Dark-state, cluster and the nano-particle that laser plasma plume brightness 9 is sent enter via secondary particle extraction field 10 to fly
In row time mass spectrum 11；Spectrometer 17 collect and be coupled to be centrally disposed perforate non-spectral instrument 17 pass through plane mirror 14, transmitting
Spectral collection system 15, be placed on 15 focal points optical fiber 16 collect laser plasma 9 emission spectrum；Flight time mass spectrum
Instrument 11 stores analysis module 18 with signal by USB interface with spectrometer 17 and is connected.
Fig. 2 is refer to, Fig. 2 is that the secondary particle of the utility model draws field structure schematic diagram.
24 ablation of ablative laser of line focus lens focus is placed on 23 shape of sample at condenser lens focal position
Into laser plasma；It is mutual with the ionization laser or resonance laser 25 and laser plasma of 24 incidence in 90 ° of ablative laser
Effect, enhancing plasma spectrometry transmitting；The first order draws field 26, the second level is drawn field 27 and connected respectively by high pressure port 29
Time of-flight mass spectrometer and two high voltage power supplies for drawing field ionization source；When electrostatic einzel lens 28 connect flight by high pressure port 29
Between mass spectrograph and draw field ionization source another high-voltage power supply；Most particle is introduced into time of-flight mass spectrometer 30 at last.
Ablative laser 24 focuses on 23 surface of sample by condenser lens, forms plasma, the second beam ionization laser or
Resonance laser 25 has the advantages of plasma carries out ionization excitation, so does again：(1), emission spectrum signal is improved；
(2), mass spectrographic resolution ratio is improved.In experimentation according to the Ultra-Violet Laser 25 that experimental duties can select photon energy high into
Row double ionization, the light fragment that ablative laser ablation 24 is come out, nano-particle, molecular cluster ionize again, realize spectrum letter
Number and mass signal optimization, and then optimize the detection limit and quantitative accuracy of quantitative detection.Laser plasma has very
High plasma exciatiaon temperature and electron density, it is each in plasma plume brightness due to the anisotropy feature of plasma
Section start location and energy are different, and particle is in the Flight Length in particle flight area 30 and time and particle initial position and energy
Measurer has very big relevance, this declines the drift for causing mass signal or resolution ratio.The utility model solves in terms of two should
Problem first, ionized again using the second beam laser 25, allows plasma plume brightness isotropism, second is that being drawn using a two level
Field design by adjusting the potential gradient drawn between field, selects suitable ratio, compensation primary power is timely to Flight Length
Between influence to mass signal, improve resolution ratio and accuracy, and then improve accuracy of quantitative analysis.
Fig. 3 is refer to, Fig. 3 is the utility model spectral collection system structure diagram.
Laser plasma 31 emits light and is reflected into convex lens 33 through plane mirror 32, and convex lens 33 will be collected into
Light, which is placed on the concavees lens 34 before concave lens focus 35 and is then coupled to, is placed on the light that convex lens 33 is formed with concavees lens 34
In optical fiber 37 at 36 position of equivalent focal length of system.
In collecting laser plasma 31 and emitting photoreduction process, experimentally simplest optical system is 38：In plasma
Between body 31 and optical fiber 37 plus a single convex lens emits light to it and is collected.In low pressure, laser plasma expands more
To be rapid, plasma plume brightness improves emission spectrum accuracy of quantitative analysis and the key point of detection limit compared with bigger under atmospheric pressure
It is：It gathers sufficiently strong spectral signal and is analyzed.In specific light path design, the numerical aperture and aperture diameter of optical fiber are
It is changeless, it, can be according to formula in order to which plasma is allowed to be all coupled to optical fiberWherein m is that this is
Optical magnification, the s of system1It is object distance, s2It is image distance, d1It is article size, d2It is the size of picture, so can root in experiment
According to distance between image, the size of object, as size lens are made choice.Because of 31 bigger of plasma ball under outer low pressure, it is
It is collected into all transmitting light, there are two types of implementation method in light path design, the first is to select short focus lens；Second is to increase
The size of big picture.First method can be realized the small purpose of image focu, but in practical applications, restrict the optical system
Another optical fiber parameter numerical aperture can limit the solid angle for collecting light, divide plasma emissioning light so as to loss section.Common light
Fine numerical aperture is 0.18-0.23, and numerical aperture is defined asWherein CA is effective thang-kng diameter, and f is
The focal length of lens, this is just obtainedAnd spectrometer could be transferred to by optical fiber by only working as the light of θ≤arcsin0.23,
This also limits the lens that cannot use excessively short focus.Second method improves the size of picture, and shortcoming is：First, valency
Lattice are expensive, optical fiber is easily contaminated, optical fiber cannot angle and curved, occupied this adds increased experimental cost and instrument empty
Between, it is not easy to integrated；Secondly as shown in optical fiber-slit coupled system 39, the slit of general spectrometer is very narrow, preferably just
Case is shown in optical fiber in Fig. 3-39 left-half of slit coupled system, and more preferably scheme is optical fiber in Fig. 3-slit coupled system
Shown in 39 center sections, if the optical fiber for selecting numerical aperture big, even if plasma optical emission can be all coupled to optical fiber, but
Most of light can also be lost by optical fiber to spectrograph slit, as shown in optical fiber -39 right half part of slit coupled system in Fig. 3.It is comprehensive
On, it is necessary to a kind of small divergence angle θ, optical system larger optical magnification m during actual experiment.The utility model
Design can solve the problems, such as this, be specially laser plasma 31 emit light converged via a convex lens, then via
One concavees lens transmitting, this can reduce angle of divergence θ.But this reduces amplification factor m, so the utility model passes through one
A plane mirror 32 extends the distance between laser plasma 31 and optical system, achievees the purpose that increase amplification factor m, from
And collect more plasma emissioning lights.In actual build process, two angled plane mirrors can also be used,
Transmitting light is allowed to be reflected once or several times between two pieces of mirrors, reaching increases amplification factor m, makes optical system imaging smaller
Purpose.In addition the plane mirror that the utility model uses can fold light path, and space can be saved during instrument is specifically built,
Convenient for integrated, portability.In conclusion the optical system of the utility model, it not only can be by collecting more plasmas
Body emits light to improve the detection limit and precision of the quantitative analytical instrument spectral analysis module, but also can fold light path and reach
It is integrated, the purpose of portability, and it is of low cost.
Application method：Quantitatively divide as shown in Figure 1, a kind of two level draws field dual-wavelength laser ablation Plasma emission spectrometry and mass spectrometry
Analysis apparatus runs automatic focusing module 1, and returns to numerical value according to it and adjust laser to the transmission instruction of the first stepper motor 6 first
Condenser lens 4, after condenser lens moves, automatic focusing module 1 sends instruction issue laser, laser warp to laser 2
Laser mirror 3 reflects and gathers the analyzed sample being placed in three-dimensional automatic sample sample platform 8 by laser line focus lens 4
Product surface forms laser plasma plumage brightness 9, while has fraction laser reflection to input laser measurement module 21, according to 21
For the numerical value laser facula of feedback to the distance L of lens, it is saturating that automatic focusing module 1 sends instructions to stepper motor adjusting focusing again
Mirror position carries out sample automatic focusing in real time, realizes the power constant in laser emission to sample, to improve quantitative point
Analyse precision.Emit laser pulse simultaneously in laser 2, laser sends a TTL trigger signal, and time-sequence control module 19 receives
After the trigger signal, according to the sequential set, 3 road TTL trigger signals are exported.Wherein first via TTL signal, triggering the
No. 2 lasers excite laser plasma again, especially in laser sensitive smooth fragment, molecular cluster, experiment
It is typically chosen the big Ultra-Violet Laser of photon energy；Second road TTL signal triggering 11 module of time of-flight mass spectrometer, laser etc. from
Daughter plumage brightness 9 draws field 10 by secondary particle and draws acceleration, and flight reaches time of-flight mass spectrometer 11；Trigger the light in 3rd tunnel
Spectrometer 17, emitted spectral collection system 15 again after the light that laser plasma plume brightness 9 emits is reflected via one piece of plane mirror 14
Optical fiber 16 is focused on, optical signal is passed to spectrometer 17 by optical fiber 16, and gathers emission spectrum signal, spectrum letter by spectrometer 17
Number and mass signal after acquisition, signal storage analysis module 18 is transferred to, by the processing of signal analysis, realizing to sample
Quantitative analysis.Due to anisotropic properties of the laser plasma in expansion process, so three-dimensional automatic sample sample platform 8 is X-
Y- θ three-dimensional platforms, so by rotating θ dimensions, so that time of-flight mass spectrometer 11 and spectrometer 17 are to different directions
9 signal collection of plasma plume brightness in order to correct quantitative analysis method, improves accuracy of quantitative analysis.It is detailed that two level draws field 10
See Fig. 2, the intensity of mass signal can be optimized by the voltage for changing two extraction fields, and mass spectrometric resolution can be improved
Rate.Emission spectrum collection system 15 refers to Fig. 3, is designed as plasma radiating light and emits via one or several plane mirrors, so
Be coupled to the optical system of a convex lens and concave lens composition afterwards, this be designed with beneficial in fixed fiber numerical aperture and
More plasma emissioning lights are collected under constant aperture diameter, so as to improve the detection of sample limit, and since signal increases
Strong optional analysis spectrum line increases, and the precision of multivariable quantitative analysis method can be improved, so as to improve analysis precision.
Finally it should be noted that：Various embodiments above is only to illustrate the technical solution of the utility model rather than it is limited
System；Although the utility model is described in detail with reference to foregoing embodiments, those of ordinary skill in the art should
Understand：It is modified to the technical solution recorded in foregoing embodiments either to which part or all technical characteristic
Equivalent substitution is carried out, the essence of appropriate technical solution is not made to depart from the scope of various embodiments of the utility model technical solution.
Claims (3)
1. a kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample, which is characterized in that automatic focusing module
(1) stepper motor (6) connected by serial ports, pass through bnc interface connecting laser (2)；Laser (2) by bnc interface and when
Sequence control module (19) connects；The laser that laser (2) is sent is via the laser mirror with incident laser direction placement at 45 °
(3), by condenser lens (4) with incident laser direction placement in 90 °, vacuum chamber form (7) and it is placed on condenser lens
(4) the sample interaction on the three-dimensional automatic sample sample platform (8) of focal point, forms laser plasma plume brightness (9)；Second
It triggers ablation and ionization laser (20) and interacts with first via incident laser angle in 90 ° and plasma plume brightness (9) in road；When
Sequence control module (19) is connected by bnc interface with time of-flight mass spectrometer (11), spectrometer (17)；Time of-flight mass spectrometer and
It draws field ionization source (12) and field (10) connection is drawn by high pressure port secondary particle；Laser plasma plume brightness (9) emits light quilt
Plane mirror (14), which will be reflected through emission spectrum collection system (15), to be emitted optically coupling in optical fiber (16)；Optical fiber (16) passes through
SMA905 interfaces will emit optical transport into spectrometer (17)；Dark-state, cluster and the nanometer that laser plasma plume brightness (9) is sent
Particle is drawn field (10) via secondary particle and is entered in time of-flight mass spectrometer (11)；Spectrometer (17) by plane mirror (14),
Emission spectrum collection system (15), optical fiber (16) the collection laser plasma for being placed on emission spectrum collection system (15) focal point
The emission spectrum of body feathers brightness (9)；Time of-flight mass spectrometer (11) passes through USB interface and signal storage analysis mould with spectrometer (17)
Block (18) connects.
2. a kind of spectrum according to claim 1 combines the quantitative analysis device of element in mass spectrographic unknown sample, special
Sign is that ablative laser (24) ablation of line focus lens focus is placed on the sample (23) at condenser lens focal position
Form laser plasma；With the ionization laser or resonance laser (25) and laser plasma of ablative laser (24) incidence in 90 °
Body interacts, enhancing plasma spectrometry transmitting；The first order draws field (26), the second level draws field (27) and passes through high pressure port
(29) connect time of-flight mass spectrometer respectively and draw two high voltage power supplies of field ionization source；Electrostatic einzel lens (28) pass through high-pressure side
Mouth (29) connection time of-flight mass spectrometer and another high-voltage power supply for drawing field ionization source；Most particle introduces flight time matter at last
In spectrometer (30).
3. a kind of spectrum according to claim 1 combines the quantitative analysis device of element in mass spectrographic unknown sample, special
Sign is that laser plasma (31) emits light and is reflected into convex lens (33) through plane mirror (32), and convex lens (33) will be received
The light collected be placed on the concavees lens (34) before concave lens focus (35) be then coupled to be placed on convex lens (33) with it is recessed
In optical fiber (37) at equivalent focal length (36) position of the optical system of mirror (34) composition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107219214A (en) * | 2017-07-26 | 2017-09-29 | 大连理工大学 | A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample |
| WO2020248812A1 (en) * | 2019-06-12 | 2020-12-17 | 大连理工大学 | Mass spectrum resolution apparatus for improving measurement of laser ablation ion species based on time-of-flight mass spectrometry |
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2017
- 2017-07-26 CN CN201720911911.9U patent/CN207396353U/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107219214A (en) * | 2017-07-26 | 2017-09-29 | 大连理工大学 | A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample |
| CN107219214B (en) * | 2017-07-26 | 2023-10-27 | 大连理工大学 | Quantitative analysis device for elements in unknown sample by spectrum combination with mass spectrum |
| WO2020248812A1 (en) * | 2019-06-12 | 2020-12-17 | 大连理工大学 | Mass spectrum resolution apparatus for improving measurement of laser ablation ion species based on time-of-flight mass spectrometry |
| EP3780066A4 (en) * | 2019-06-12 | 2021-07-21 | Dalian University of Technology | Mass spectrum resolution apparatus for improving measurement of laser ablation ion species based on time-of-flight mass spectrometry |
| US11087966B1 (en) | 2019-06-12 | 2021-08-10 | Dalian University Of Technology | Mass spectrum resolution device for measuring laser ablation ion species with improved time of flight mass spectrometry |
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