CN115376881B - Double-optical-path time delay adjustable device for double-beam laser mass spectrum ionization source - Google Patents

Double-optical-path time delay adjustable device for double-beam laser mass spectrum ionization source Download PDF

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CN115376881B
CN115376881B CN202211230748.1A CN202211230748A CN115376881B CN 115376881 B CN115376881 B CN 115376881B CN 202211230748 A CN202211230748 A CN 202211230748A CN 115376881 B CN115376881 B CN 115376881B
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laser
polarization
module
light
dual
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CN115376881A (en
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王小磊
成巍
马新强
任远
王靖雯
戈海龙
李文龙
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Laser Institute of Shandong Academy of Science
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Laser Institute of Shandong Academy of Science
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns
    • H01J49/16Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/164Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/64Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/28Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
    • G02B27/283Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising used for beam splitting or combining
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/28Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
    • G02B27/286Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising for controlling or changing the state of polarisation, e.g. transforming one polarisation state into another

Abstract

The invention belongs to the technical field of dual-beam laser mass spectrometry ionization equipment, and relates to a dual-optical-path delay adjustable device for a dual-beam laser mass spectrometry ionization source, which comprises a pulse delay generator, a laser driving power supply, a laser, a high-voltage pressurizing module, a polarization modulation module, a polarization splitting module B, a first optical path and a second optical path; the pulse delay generator is used for sending a zero-time signal to the laser driving power supply and sending a pressurizing trigger signal to the high-voltage module; the laser driving power supply is used for controlling the laser to work; the high-voltage module is used for applying half-wave voltage to the polarization modulation module; when the polarization modulation module is applied with half-wave voltage, the polarization direction of light is changed by 90 degrees; the laser output by the laser reaches the polarization beam splitting module B through the polarization modulation module, and the polarization beam splitting module B guides the laser in the first linear polarization state to the first optical path and guides the laser in the second polarization state to the second optical path. The invention realizes the double-step laser mass spectrometry method by only one laser, and the equipment volume is small.

Description

Double-light-path delay adjustable device for ionization source of double-beam laser mass spectrometer
Technical Field
The invention belongs to the technical field of dual-beam laser mass spectrometry ionization equipment, and particularly relates to a dual-optical-path delay adjustable device for a dual-beam laser mass spectrometry ionization source.
Background
The laser ionization technology is widely applied to the field of mass spectrometry, single-beam laser irradiation is adopted in laser desorption ionization mass spectrometry detection, the ionization efficiency of a sample is low, and a two-step laser mass spectrometry is developed in the 80 th of the 20 th century in order to improve the ionization efficiency of the sample.
The principle of the two-step laser mass spectrometry is as follows: irradiating the first beam of laser onto the substrate carrying the sample, instantly desorbing and ionizing the sample for one time to form an air mass in a range of 0.5-2mm away from the surface of the target body; after a certain time delay, the second beam of laser irradiates the air mass to ionize the sample molecules for the second time, so that the ionization efficiency of the sample is improved; the ionized ions are then introduced into a mass spectrometer for detection.
The two lasers in the double-step laser mass spectrometry act in mutually independent time and space, so that the double-beam laser mass spectrometry ionization device in the prior art needs two lasers to respectively generate two beams of pulse lasers, and a digital delay pulse generator is adopted to control the delay time between the two beams of pulse lasers, which causes the double-beam laser mass spectrometry ionization device to have larger volume, complex system and higher cost.
Disclosure of Invention
The invention aims to solve the technical problem of making up the defects of the prior art and provides a double-optical-path delay adjustable device for a double-beam laser mass spectrometry ionization source so as to reduce the cost and the size of the device.
To solve the technical problems, the technical scheme of the invention is as follows:
a double-optical-path time delay adjustable device for a double-beam laser mass spectrum ionization source comprises a pulse time delay generator, a laser driving power supply, a laser, a high-voltage pressurizing module, a polarization modulation module, a polarization light splitting module B, a first optical path and a second optical path;
the pulse delay generator is used for sending a zero-time signal to the laser driving power supply and is also used for sending a pressurizing trigger signal to the high-voltage pressurizing module;
the laser driving power supply is used for starting and controlling the laser to work when receiving a zero-time signal;
the laser has output wavelength of lambda and pulse width of t 1 Having a period of T 1 The pulsed laser of (1);
the high-voltage pressurizing module is used for applying half-wave voltage to the polarization modulation module when receiving a pressurizing trigger signal;
when the polarization modulation module is applied with half-wave voltage, the polarization direction of the polarized laser passing through the polarization modulation module changes by 90 degrees;
the polarization light splitting module B is used for transmitting the light in the first linear polarization state and reflecting the light in the second polarization state;
pulse laser output by the laser reaches the polarization beam splitting module B through the polarization modulation module, the polarization beam splitting module B guides the laser in the first linear polarization state to the first optical path, and guides the laser in the second polarization state to the second optical path;
the first optical path is used for outputting desorption light and irradiating the desorption light to the upper surface of the sample target plate at an angle alpha, wherein alpha is more than 0 degrees and less than 90 degrees;
the second light path is used for outputting ionizing light, the ionizing light is parallel to the upper surface of the sample target plate, and the distance between the ionizing light and the upper surface of the sample target plate is 0.5-2mm.
Further, the working principle comprises the following steps:
s1: the working period duration of the pulse delay generator is adjusted to be T by people 2 Duration of the working cycle T 2 Including a delay time period t 2 The number of working cycles is P;
s2: starting a pulse delay generator, wherein the pulse delay generator sends a zero-time signal to a laser driving power supply, and the laser driving power supply starts and controls a laser to output laser when receiving the zero-time signal; when the pulse delay generator sends a zero-time signal, the first working period T is started 2
S3: the work cycle of the pulse delay generator is as follows: delay t of pulse delay generator 2 ,t 2 Within a time duration, the pulse emitted by the laser is n 1 N is 1 Outputting the laser pulse through a first optical path; pulse delay generator completes delay time t 2 When the voltage is applied to the polarization modulation module, the pulse delay generator sends a pressurizing trigger signal to the high-voltage pressurizing module, the high-voltage pressurizing module applies half-wave voltage to the polarization modulation module when receiving the pressurizing trigger signal, and the pressurizing time length is t 3 ,t 3 >t 1 And t is 3 =T 2 -t 2 ;t 3 Duration of timeThe pulse emitted by the laser is n 2 N is 2 Outputting the laser pulse through a second optical path;
s4: and (4) the pulse delay generator starts the next working period, the step (S3) is repeated, when the pulse delay generator finishes the P-th working period, a work stopping signal is sent to the laser driving power supply, then the pulse delay generator stops working, and when the laser driving power supply receives the work stopping signal, the laser is controlled to stop emitting light.
Further, in the step S3, the rising edge time of the half-wave voltage is less than 20ns.
Furthermore, the polarization beam splitter further comprises a lambda/2 wave plate and a polarization beam splitting module A which are sequentially arranged behind the light outlet of the laser, so that the laser sequentially passes through the lambda/2 wave plate, the polarization beam splitting module A and the polarization modulation module to reach the polarization beam splitting module B.
Further, the polarization beam splitting module a and the polarization beam splitting module B are one of a thin film polarizer, a polarization beam splitting prism, a glan taylor prism, and a roche prism.
Further, the laser outputs a pulse laser wavelength λ of one of 515 nm, 532 nm, 1030 nm, and 1064 nm.
Further, the polarization modulation module is one of an electro-optical crystal RTP, DKDP and LN.
Further, the first optical path sequentially includes a first wavelength conversion module, a first lens, and a first reflector; the second optical path comprises a second wavelength conversion module, a second reflector and a second lens in sequence.
Further, the first wavelength conversion module and the second wavelength conversion module are composed of a second-order nonlinear crystal or a third-order nonlinear crystal.
Further, the second order nonlinear crystal is one or more of KTP crystal, LBO crystal, BBO crystal and CLBO crystal, and the third order nonlinear crystal is Ba (NO) 3 ) 2 、YVO 4 One of the crystals.
The invention can achieve the following beneficial effects:
(1) Through the matching use of pulse delay generator, high-pressure pressurization module, laser instrument drive power supply, laser instrument, polarization modulation module, polarization beam splitting module, realized only realizing two step laser mass spectrography through a laser instrument, realized two bundles of laser promptly all mutually independent in time and space, compare with two laser instruments realization two step laser mass spectrography among the prior art, the light path switching time is short, and the cost is reduced has reduced the equipment volume.
(2) Working period duration T of pulse delay generator 2 And a delay time period t 2 The time length can be adjusted according to practical application, can be microsecond or nanosecond, the size of the equipment cannot be changed by adjusting the time length, and the sample is suitable for a wide range of types.
Drawings
FIG. 1 is a schematic diagram of the construction of an embodiment of the present invention;
FIG. 2 is a schematic diagram of the optical path of an embodiment of the present invention;
FIG. 3 is a schematic diagram of a pulse sequence according to an embodiment of the present invention;
FIG. 4 is a control flow diagram of an embodiment of the present invention;
in the figure: the device comprises a 1-lambda/2 wave plate, a 2-polarization light splitting module A, a 3-polarization modulation module, a 4-polarization light splitting module B, a 5-LBO crystal A, a 6-LBO crystal B, a 7-first lens, an 8-first reflector, a 9-sample target plate, a 10-second lens, a 11-second reflector, a 12-BBO crystal and a 13-LBO crystal C.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
A double-optical-path delay adjustable device for a double-beam laser mass spectrometry ionization source comprises a pulse delay generator, a high-voltage pressurizing module, a laser driving power supply, a laser, a lambda/2 wave plate 1, a polarization light splitting module A2, a polarization modulation module 3, a polarization light splitting module B4, a first optical path and a second optical path;
the pulse delay generator is used for sending a zero-time signal to the laser driving power supply and is also used for sending a pressurizing trigger signal to the high-voltage pressurizing module;
the laser driving power supply is used for starting and controlling the laser to work when receiving a zero-time signal;
the laser has output wavelength of lambda and pulse width of t 1 Having a period of T 1 The pulse laser of (1), the pulse laser being linearly polarized light;
the lambda/2 wave plate 1 is used for enabling the polarization direction of linearly polarized light emitted by the laser to rotate to be consistent with the transmission polarization direction of the polarization splitting module A2;
the high-voltage pressurizing module is used for applying half-wave voltage to the polarization modulation module when receiving a pressurizing trigger signal;
when the polarization modulation module is applied with half-wave voltage, the polarization direction of the polarized laser passing through the polarization modulation module is changed by 90 degrees and becomes vertical polarized light;
the polarization light splitting module B is used for transmitting light in a first polarization state (i.e. horizontally polarized light) and reflecting light in a second polarization state (i.e. vertically polarized light);
pulse laser output by the laser reaches a polarization beam splitting module B through a polarization modulation module, the polarization beam splitting module B guides laser in a first linear polarization state (namely horizontal polarization light) to a first optical path, and guides laser in a second polarization state (namely vertical polarization light) to a second optical path;
the first optical path is used for outputting desorption light and irradiating the desorption light to the upper surface of the sample target plate 9 at an angle alpha, wherein alpha is more than 0 degrees and less than 90 degrees; the desorption light is used for desorbing and ionizing the sample molecules for the first time;
the second light path is used for outputting ionizing light, the ionizing light is parallel to the upper surface of the sample target plate 9, and the distance between the ionizing light and the upper surface of the sample target plate 9 is 0.5-2mm; the ionized light is used for carrying out secondary ionization on the gas-phase biomolecules, and the sample target plate 9 is used for carrying a sample.
In this embodiment, the polarization splitting module A2 and the polarization splitting module B4 are both polarization splitting Prisms (PBS), and of course, under the guidance of this embodiment, a person skilled in the art may select one of a thin film polarizer, a glantle prism, and a roche prism instead of the polarization splitting Prism (PBS).
In this embodiment, the pulse laser wavelength λ output by the laser is 1064 nm, and certainly, a person skilled in the art may select the pulse laser wavelength λ as one of 515 nm, 532 nm, and 1030 nm according to actual requirements.
In this embodiment, the polarization modulation module 3 is an electro-optical crystal RTP (rubidium, oxygen, titanium, and phosphate-based phosphate) crystal, and of course, a person skilled in the art may select one of a DKDP (potassium dideuterium phosphate) crystal and an LN (lithium niobate) crystal to replace the electro-optical crystal RTP;
a high-pressure pressurizing module: by applying an electric field to the electro-optic crystal, the refractive index of the crystal is changed along with the applied electric field by utilizing the linear electro-optic effect of the electro-optic crystal, namely the Pockels effect, and the polarization state of laser passing through the crystal is changed by controlling high voltage applied to two ends of the electro-optic crystal.
The first optical path in this embodiment sequentially includes a first wavelength conversion module, a first lens 7, and a first reflector 8, where the first wavelength conversion module sequentially includes an LBO crystal A5 and an LBO crystal B6, and generates a frequency doubling and sum frequency effect on incident light; the light sequentially passes through the LBO crystal A5, the LBO crystal B6, the first lens 7 and the first reflector 8, and then irradiates the upper surface of the substrate of the sample target plate 9 at an angle of 45 degrees to form desorption light, and the wavelength of the desorption light is 355nm. Under the guidance of this example, one skilled in the art can select the desorbing light to be ultraviolet, visible, near infrared or mid infrared laser light with a wavelength range of 355nm to 3000nm.
The second optical path in this embodiment sequentially includes a second wavelength conversion module, a second reflector 11, and a second lens 10, where the second wavelength conversion module sequentially includes an LBO crystal C13 and a BBO crystal 12, and generates a frequency doubling and frequency quadrupling effect on incident light; the light passes through LBO crystal C13, BBO crystal 12, second reflector 11 and second lens 10 in sequence, and then is emitted out in parallel with the upper surface of the sample target plate 9 to be ionized light, the wavelength of the ionized light is 266nm, the distance between the ionized light and the upper surface of the sample target plate 9 is 0.5-2mm, and the ionized light is emitted into gas-phase sample molecules. The ionizing light is typically ultraviolet light, and those skilled in the art can select the wavelength range of 200-355nm from the light under the guidance of this example.
In the present embodiment, the fingerIn other words, one skilled in the art can select the first wavelength conversion module and the second wavelength conversion module to be composed of a second-order nonlinear crystal or a third-order nonlinear crystal according to the actual wavelength conversion requirement, where the second-order nonlinear crystal is KTP (potassium titanyl phosphate) crystal, LBO (lithium triborate) crystal, BBO (β -phase barium metaborate) crystal, CLBO (cesium lithium borate) crystal, and the third-order nonlinear crystal can be Ba (NO) (NO cesium lithium borate) 3 ) 2 Barium nitrate, YVO 4 (Yttrium vanadate).
Referring to fig. 1-4, the working principle of the present embodiment includes the following steps:
s1: the working period duration of the pulse delay generator is adjusted to be T by people 2 Duration of the working cycle T 2 Including a delay period t 2 The number of the working cycles is P;
s2: starting a pulse delay generator, wherein the pulse delay generator sends a zero-time signal to a laser driving power supply, and the laser driving power supply starts to control a laser to output laser when receiving the zero-time signal; the pulse delay generator starts a first working period T when sending a zero-time signal 2
S3: the work cycle of the pulse delay generator is as follows: delay t of pulse delay generator 2 ,t 2 Within a time duration, the pulse emitted by the laser is n 1 N is 1 After passing through the polarization modulation module 3, the laser pulse still keeps the original polarization direction, namely horizontal polarized light, then passes through the polarization light splitting module B4, and is output through a first light path; pulse delay generator completes delay time t 2 When the voltage is applied to the polarization modulation module, the pulse delay generator sends a pressurizing trigger signal to the high-voltage pressurizing module, the high-voltage pressurizing module applies half-wave voltage to the polarization modulation module when receiving the pressurizing trigger signal, and the pressurizing time length is t 3 ,t 3 >t 1 And t is 3 =T 2 -t 2 ;t 3 Within a time duration, the laser emits a pulse of n 2 After n2 laser pulses pass through the polarization modulation module 3, the polarization direction changes by 90 degrees, namely, the laser pulses are changed into vertical polarized light, and then the vertical polarized light is reflected to a second light path by the polarization light splitting module B4 and is output through the second light path;
s4: and (4) the pulse delay generator starts the next working period, the step (S3) is repeated, when the pulse delay generator finishes the P-th working period, a work stopping signal is sent to the laser driving power supply, then the pulse delay generator stops working, and when the laser driving power supply receives the work stopping signal, the laser is controlled to stop emitting light.
The polarization splitting module A2 is arranged to enable the purity of the polarized laser light output by the laser to be higher.
In the description of the present invention, words such as "inner", "outer", "upper", "lower", "front", "rear", etc., indicating orientations or positional relationships, are used for convenience in describing the present invention, and do not indicate or imply that the indicated device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
The above description is only one embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the spirit of the present invention.

Claims (9)

1. A double-optical-path time delay adjustable device for a double-beam laser mass spectrum ionization source is characterized in that: the device comprises a pulse delay generator, a laser driving power supply, a laser, a high-voltage pressurizing module, a polarization modulation module, a polarization light splitting module B, a first light path and a second light path;
the pulse delay generator is used for sending a zero-time signal to the laser driving power supply and is also used for sending a pressurizing trigger signal to the high-voltage pressurizing module;
the laser driving power supply is used for starting and controlling the laser to work when receiving a zero-time signal;
the laser has output wavelength of lambda and pulse width of t 1 Having a period of T 1 The pulsed laser of (1);
the high-voltage pressurizing module is used for applying half-wave voltage to the polarization modulation module when receiving a pressurizing trigger signal;
when the polarization modulation module is applied with half-wave voltage, the polarization direction of the polarized laser passing through the polarization modulation module changes by 90 degrees;
the polarization light splitting module B is used for enabling light in a first linear polarization state to transmit and enabling light in a second polarization state to reflect;
pulse laser output by the laser reaches the polarization beam splitting module B through the polarization modulation module, the polarization beam splitting module B guides the laser in the first linear polarization state to the first optical path, and guides the laser in the second polarization state to the second optical path;
the first optical path is used for outputting desorption light and irradiating the desorption light to the upper surface of the sample target plate at an angle alpha, wherein alpha is more than 0 degrees and less than 90 degrees;
the second light path is used for outputting ionizing light, the ionizing light is parallel to the upper surface of the sample target plate, and the distance between the ionizing light and the upper surface of the sample target plate is 0.5-2mm;
the working principle comprises the following steps:
s1: the working period duration of the pulse delay generator is adjusted to be T manually 2 Duration of the working cycle T 2 Including a delay time period t 2 The number of the working cycles is P;
s2: starting a pulse delay generator, wherein the pulse delay generator sends a zero-time signal to a laser driving power supply, and the laser driving power supply starts and controls a laser to output laser when receiving the zero-time signal; the pulse delay generator starts a first working period T when sending a zero-time signal 2
S3: the work cycle of the pulse delay generator is as follows: delay t of pulse delay generator 2 ,t 2 Within a time duration, the pulse emitted by the laser is n 1 N is 1 Outputting the laser pulse through a first optical path; pulse delay generator completes delay time t 2 When the voltage is applied to the polarization modulation module, the pulse delay generator sends a pressurizing trigger signal to the high-voltage pressurizing module, and the high-voltage pressurizing module applies half-wave voltage to the polarization modulation module when receiving the pressurizing trigger signal, wherein the pressurizing time length is t 3 ,t 3 >t 1 And t is 3 =T 2 -t 2 ;t 3 Within a time duration, the pulse emitted by the laser is n 2 N is 2 Outputting the laser pulse through a second optical path;
s4: and (4) the pulse delay generator starts the next working period, the step (S3) is repeated, when the pulse delay generator finishes the P-th working period, a work stopping signal is sent to the laser driving power supply, then the pulse delay generator stops working, and when the laser driving power supply receives the work stopping signal, the laser is controlled to stop emitting light.
2. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 1, which is characterized in that: in the step S3, the rising edge time of the half-wave voltage is less than 20ns.
3. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 1, which is characterized in that: the laser device also comprises a lambda/2 wave plate and a polarization beam splitting module A which are sequentially arranged behind the light outlet of the laser device, so that the laser passes through the lambda/2 wave plate, the polarization beam splitting module A and the polarization modulation module in sequence and reaches the polarization beam splitting module B.
4. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 3, which is characterized in that: the polarization light splitting module A and the polarization light splitting module B are one of a film polaroid, a polarization light splitting prism, a Glan Taylor prism and a Luo Jie prism.
5. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 1, which is characterized in that: the laser outputs a pulse laser wavelength lambda of one of 515 nm, 532 nm, 1030 nm and 1064 nm.
6. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 1, characterized in that: the polarization modulation module is one of an electro-optical crystal RTP, a DKDP and an LN.
7. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 1, which is characterized in that: the first optical path sequentially comprises a first wavelength conversion module, a first lens and a first reflector; the second optical path comprises a second wavelength conversion module, a second reflector and a second lens in sequence.
8. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 7, wherein: the first wavelength conversion module and the second wavelength conversion module are composed of second-order nonlinear crystals or third-order nonlinear crystals.
9. The dual-optical-path delay adjustable device for the dual-beam laser mass spectrometry ionization source of claim 8, wherein: the second order nonlinear crystal is one or more of KTP crystal, LBO crystal, BBO crystal and CLBO crystal, and the third order nonlinear crystal is Ba (NO) 3 ) 2 、YVO 4 One of the crystals.
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