CN107677601A - The decay for detecting micro liquid Terahertz wave spectrum is totally reflected micro-fluidic prism and preparation method - Google Patents

The decay for detecting micro liquid Terahertz wave spectrum is totally reflected micro-fluidic prism and preparation method Download PDF

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CN107677601A
CN107677601A CN201710994968.4A CN201710994968A CN107677601A CN 107677601 A CN107677601 A CN 107677601A CN 201710994968 A CN201710994968 A CN 201710994968A CN 107677601 A CN107677601 A CN 107677601A
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micro
prism
decay
sample
cover plate
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CN107677601B (en
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张明焜
魏东山
杨忠波
汤明杰
颜识涵
张华�
王化斌
崔洪亮
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Chongqing Institute of Green and Intelligent Technology of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3581Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
    • G01N21/3586Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]

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Abstract

The present invention relates to a kind of decay for detecting micro liquid Terahertz wave spectrum to be totally reflected micro-fluidic prism and preparation method, belongs to liquid phase sample Terahertz wave spectrum detection technique field.Comprising decay total reflection prism main body, cover plate, decay total reflection prism main body is in triangular prism shaped, and in three cylinders, one of rectangular surfaces are fully reflecting surface, and remaining two rectangular surfaces are THz wave coupling surface;Cover plate is arranged on fully reflecting surface, and micro-channel structure is provided with the surface of cover plate, is additionally provided with through hole and is used to connect micro-channel structure, through hole is used for the sample introduction of liquid or goes out sample, and cover plate is brought into close contact with fully reflecting surface.The sample size that conventional droop total reflection mode detects is reduced to tens microlitres by the present invention, is especially suitable for the detection of valuable sample, rare sample;Fluid to be measured is sealed by miniflow simultaneously, is especially suitable for the detection of volatile sample, poisonous and harmful sample.

Description

The decay for detecting micro liquid Terahertz wave spectrum is totally reflected micro-fluidic prism and making Method
Technical field
The invention belongs to liquid phase sample Terahertz wave spectrum detection technique field, is related to a kind of detection micro liquid THz wave The decay of spectrum is totally reflected micro-fluidic prism and preparation method.
Background technology
THz wave spectral technology is widely used to all kinds of biochemistry detection fields.Attenuated total reflectance be liquid sample too A kind of effective ways of hertz wave spectrum detection.Decay total reflection is between the evanescent wave and sample on measurement total reflection prism surface Interactive information, produce and the similar spectrogram of transmission absorption.Evanescent wave is tangentially propagated along interface and with from crystal outer surface Distance increase and amplitude is exponentially decayed.In terahertz wave band, evanescent wave can be with tens to hundreds of microns above fully reflecting surface Liquid effects, by analyze outgoing terahertz wave signal, the Terahertz physical property with regard to liquid sample can be obtained.Same Under detection instrument, it is only relevant with the refractive index and Terahertz frequency of liquid to penetrate the evanescent wave of liquid sample, with sample thickness without Close, avoiding problems accurate the problem of controlling and measuring thickness of liquid film is needed when transmission mode detects.Meanwhile reflective detection The interference of standing wave resonance will not be brought, simplifies the post processing flow of data.
Described above, decay total reflection has obvious advantage in the detection of liquid sample.However, because decay is all-trans It is in hydrophobicity to penetrate silicon, germanium material that prism is commonly used, and the sample for generally requiring the μ L of injection 200~800 just can guarantee that liquid soaks completely Moisten whole fully reflecting surface, to ensure the Stability and veracity of measurement.Detection of the detection limit for rare sample, valuable sample The high height of cost.In addition, the liquid carrying pond of in general decay total reflection prism is open architecture, it is unfavorable for volatile sample, has The detection of the harmful sample of poison.
The content of the invention
In view of this, it is an object of the invention to provide a kind of decay total reflection for detecting micro liquid Terahertz wave spectrum is micro- Stream control prism and preparation method, are reduced to tens microlitres by the sample size that conventional droop total reflection mode detects, are especially suitable for expensive Same, the detection of rare sample;Fluid to be measured is sealed by fluid channel simultaneously, is especially suitable for volatile sample, poisonous and harmful The detection of sample.
To reach above-mentioned purpose, the present invention provides following technical scheme:
A kind of decay for detecting micro liquid Terahertz wave spectrum is totally reflected micro-fluidic prism, includes decay total reflection prism master Body 1, cover plate 2, the decay total reflection prism main body 1 is in triangular prism shaped, and in three cylinders, one of rectangular surfaces are to be all-trans Face 12 is penetrated, remaining two rectangular surfaces are THz wave coupling surface 11;
The cover plate 2 is arranged on the fully reflecting surface 12, and micro-channel structure 21 is provided with the surface of the cover plate 2, Be provided with through hole 22 in the micro-channel structure 21, the through hole 22 is used for the sample introduction of liquid or goes out sample, the cover plate 2 with it is described Fully reflecting surface 12 is brought into close contact.
Further, the decay total reflection prism main body 1 is made up of silicon crystal or germanium crystal material, and the cover plate is by poly- two Methylsiloxane material is made.
Further, the surface figure accuracy of the THz wave coupling surface 11 is less than 500nm, and surface roughness is less than 100nm, entirely The incidence angle of reflecting surface 12 is more than critical internal reflection angle.
Further, the area of the micro-channel structure 21 is more than Terahertz hot spot, and the depth of micro-channel structure 21 is with suddenly dying Ripple penetration depth matches.
Further, the calculation formula of the critical internal reflection angle is as follows:
Wherein:θcFor critical internal reflection angle, nSolFor the refractive index of fluid sample, ncFor the refractive index of prism material of main part.
The preparation method of micro-fluidic prism, is comprised the following steps:
S1:A burnishing surface for selecting silicon crystal or germanium crystal is fully reflecting surface;
S2:The incidence angle of wave beam coupling surface is designed, and by cutting, wet etching, polishes and Terahertz is made on crystal Ripple coupling surface, complete the making of decay total reflection prism main body;
S3:The planar graph of fluid channel is designed, and makes photo mask board;
S4:The male structure of fluid channel figure is made in substrate by photoetching process, the male template needed for injection is made;
S5:The prepolymer of dimethyl silicone polymer and crosslinking agent are well mixed, and dimethyl silicone polymer is uniformly filled After horizontal rest solidification, dimethyl silicone polymer piece is taken off from male template in male template for note;
S6:Through hole is made on dimethyl silicone polymer piece, completes the making of cover plate;
S7:By oxygen plasma bonding or thermal bonding method, by the decay total reflection prism main body and S6 in S2 Cover plate is brought into close contact, and forms the flow passage structure of sealing.
Further, in step S4, the height of the male structure is 50-200 μm.
Further, the thickness for the dimethyl silicone polymer being poured in step S5 in male template is 2-5mm.
The beneficial effects of the present invention are:
1st, using the present invention, the Terahertz wave spectrum of liquid sample can be detected by attenuated total reflectance, and obtains multiple be situated between The physical parameters such as electric constant, refractive index, absorption coefficient.
2nd, using the present invention, sample size can be reduced to tens microlitres, saved existing decay total reflection detection mode institute The sample size needed, reduces valuable sample, the testing cost of rare sample.Tested sample is sealed by fluid channel simultaneously, avoided Contact of the liquid with ambient atmosphere, realize the Terahertz wave spectrum detection to volatile sample, poisonous and harmful sample.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out Explanation:
Fig. 1 is the structural representation that decay of the embodiment of the present invention is totally reflected micro-fluidic prism;
Fig. 2 is the operation principle schematic diagram that decay of the embodiment of the present invention is totally reflected micro-fluidic prism;
Fig. 3 is the engineering drawing that decay of the embodiment of the present invention is totally reflected micro-fluidic prism;
Fig. 4 is that the decay of the embodiment of the present invention is totally reflected micro-fluidic prism detection ethanol, the design sketch of acetone equal samples.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
As shown in figure 1, the present invention is totally reflected micro-fluidic prism for a kind of decay, decay total reflection prism main body 1, lid are included Piece 2, decay total reflection prism main body 1 is in triangular prism shaped, and in three cylinders, one of rectangular surfaces are fully reflecting surface 12, is remained Two rectangular surfaces of remaininging are THz wave coupling surface 11;
Cover plate 2 is arranged on fully reflecting surface, and micro-channel structure 21 is provided with the surface of cover plate 2, is additionally provided with least two Individual through hole 22 runs through micro-channel structure 21, and through hole 22 is used for the sample introduction of liquid or goes out sample, and cover plate 2 closely pastes with fully reflecting surface 12 Close.
The recessed structure 21 of fluid channel may be configured as rhombus, circle or other shapes, and its shape area should be greater than Terahertz hot spot, It is chosen as 3.0~5.0cm2, depth should match with evanescent wave penetration depth, be chosen as 50~200 μm.
Prism main body 1 typically chooses silicon, germanium crystal, and the cover plate 2 typically chooses polydimethyl siloxane material.
From material of High Resistivity Si of the resistivity more than 3000 Ω cm as prism main body in the present embodiment.According to terahertz Hereby spot size, in order that Terahertz hot spot is projected on coupling surface completely, intend choosing the body that 65mm is long, 40mm is wide, 25mm is thick Silicon;
Determine the incidence angle of fully reflecting surface, relation is as follows:
N in above formulaSol、nSiThe respectively refractive index of liquid sample and silicon.N in this exampleSolFor 1.0~2.5, nSiFor 3.4, to meet still to be totally reflected under maximum sample refractive index, interface critical angle of incidence θ must be totally reflected by calculatingcFor 47.3 °, The incidence angle θ that fully reflecting surface is chosen in this example is 51.6 °, as shown in Figure 2.
Determine the inclination angle of wave beam coupling surfaceMicro-fluidic prism levels are placed during detection, terahertz wave beam glancing incidence, According to geometrical relationship, Terahertz coupling surface drift angle can be obtainedFor 38.4 °, as shown in Fig. 3 I.
Determine fluid channel depth d, penetration depth d of the evanescent wave in silicon-liquid surfacepIt is as follows with the relation of wavelength X:
D in above formulapFeature penetration depth when decaying to the 1/e at surface for the electric-field intensity of THz wave, the present invention It is evanescent wave penetration depth to think the depth, and λ is incidence wave wavelength, and θ is the incidence angle at total reflection interface.Then 0.1~ Evanescent wave penetration depth under 10.0THz wave bands is in tens to hundreds of micron, and therefore, it is 100 μm that this example, which chooses flow channel depth d,.
The preparation method that decay is totally reflected micro-fluidic prism is as follows:
1) burnishing surface for selecting crystalline silicon 40mm*65mm is fully reflecting surface.
2) inclined-plane that drift angle is 38.4 ° and polishing are cut on two 40mm*25mm face, surface figure accuracy is formed and is less than 500nm, surface roughness are less than 100nm THz wave coupling surface.
3) planar graph of design rounded diamond fluid channel, rhombus length of side 19.0mm, left and right radius of corner 10.0mm, up and down Radius of corner 5.0mm, the circular diameter 3.0mm of tangent line half, and make photo mask board with laser writing technology;
4) SU-8 photoresists of the μ m-thick of spin coating 100 on a quartz substrate, formed by exposure, development step on substrate micro- The male structure of runner pattern, the template as injection cover plate.
5) by polydimethylsiloxane prepolymer thing and crosslinking agent with 10:1 volume ratio is mixed and stirred for uniformly, thing to be mixed In bubble be wholly absent after, be poured in the template described in step 4), the thickness control of dimethyl silicone polymer in 2~5mm, Horizontal rest takes off dimethyl silicone polymer piece after dimethyl silicone polymer solidification from template.
6) in the design attitude a diameter of 2mm of the card punch making through hole of dimethyl silicone polymer piece, connect with fluid channel It is logical, the sample introduction/go out sample through hole as sample.
7) prism main body and cover plate are put into plasma washing machine, it should be noted that the fully reflecting surface of prism upward, cover plate Flow passage structure it is face-up.After being handled 1 minute with oxygen plasma, the complete of prism main body is close in the face that cover plate has flow passage structure Reflecting surface, and apply certain pressure, completion cover plate is bonded with prism main body, forms the flow passage structure of sealing.
Prepared micro-fluidic prism is as shown in figure 1, wherein 1 represents prism main body, and 2 represent cover plate, and 11 represent Terahertz Ripple coupling surface, 12 represent fully reflecting surface, and 21 represent the recessed structure of fluid channel, and 22 represent through hole.Wherein Fig. 3 represents micro-fluidic prism The front view of engineering drawing I, II side view, III top view, the partial view of IV front view identification division.
Adjust the position of THz wave transmitting antenna and reception antenna, it is P polarization to make THz wave, and by transmitting antenna, Micro-fluidic prism, reception antenna are adjusted to same horizontal line, adjust the time delay of terahertz time-domain spectroscopy instrument, obtain Terahertz letter Number.
The air humidity of test environment is controlled, being filled with drying nitrogen in environment is detected drops below relative humidity 3%, the electric field magnitude E now exportedRefFor reference signal.
About 50 μ L liquid sample is injected in the runner of micro-fluidic prism by micro fluid dynamcis system, now Terahertz Outgoing signal can substantially change, the electric field magnitude E now exportedSamFor sample signal.
If the electric field magnitude of incident THz wave is EIn, then according to reflection law:
R in formulaRefFor unimplanted sample when reflectance factor, the as reflectance factor at silicon-nitrogen interface in this example;rSam For the reflectance factor after injection fluid sample.
Again according to Fresnel reflection law, reflectance factor r of the silicon-liquid surface under P polarization12It is illustrated in figure 2
ε in formulaSiFor the complex dielectric permittivity of silicon prism, ε is the complex dielectric permittivity for the material for being close to fully reflecting surface, i.e., unimplanted It is nitrogen during sample, is filled with after liquid sample as the complex dielectric permittivity of sample.Liquid-runner upper wall surface interface is under P polarization Reflectance factor r23, it is illustrated in figure 2
ε in formulawFor the complex dielectric permittivity of runner upper wall surface.Then simultaneous (4) (5) formula can obtain rSamFor
D is flow channel depth in formula, as shown in Fig. 2 simultaneous (3) (6) formula can solve the complex dielectric permittivity ε of liquid sample.
Fig. 2 represents that decay is totally reflected micro-fluidic prism operation principle schematic diagram.Wherein:1 represents prism main body, and 2 represent lid Piece, 3 represent incident THz wave, and 4 represent outgoing THz wave, and 5 represent liquid sample, and 6 represent evanescent wave.
Propagation of the terahertz wave beam in micro-fluidic prism is as described below.Micro-fluidic prism levels are placed, THz wave Transmitting terminal projects the level of terahertz wave beam 3 on one coupling surface 11 of prism, and THz wave is by nitrogen-prism boundary folding Enter after penetrating in prism, and project fully reflecting surface 12, THz wave experiences total internal reflection on fully reflecting surface.In higher frequency band On, the evanescent wave on interface acts on liquid sample completely;On compared with low-frequency range, the evanescent wave and liquid sample on interface are mutual After effect, liquid surface and runner wall action are penetrated again, as shown in Fig. 36.Last terahertz wave beam 4 reflexes to offside On coupling surface, after prism-nitrogen interfacial refraction, level is injected on detector.Now, the terahertz wave beam of outgoing is mainly taken The information of carrying liqs sample.
Ethanol, acetone liquid are detected successively according to above-mentioned steps, the result of acquisition is as shown in Figure 4.
Finally illustrate, preferred embodiment above only to illustrate invention technical scheme and it is unrestricted, although passing through The present invention is described in detail for above preferred embodiment, it is to be understood by those skilled in the art that can be in shape Various changes are made in formula and to it in details, without departing from claims of the present invention limited range.

Claims (8)

1. a kind of decay for detecting micro liquid Terahertz wave spectrum is totally reflected micro-fluidic prism, it is characterised in that:It is complete comprising decay Reflecting prism main body (1), cover plate (2), the decay total reflection prism main body (1) is in triangular prism shaped, in three cylinders, wherein One rectangular surfaces is fully reflecting surface (12), and remaining two rectangular surfaces are THz wave coupling surface (11);
The cover plate (2) is arranged on the fully reflecting surface (12), and micro-channel structure is provided with the surface of the cover plate (2) (21) through hole (22), is provided with the micro-channel structure (21), the through hole (22) is used for the sample introduction of liquid or goes out sample, described Cover plate (2) is brought into close contact with the fully reflecting surface (12).
2. a kind of decay for detecting micro liquid Terahertz wave spectrum according to claim 1 is totally reflected micro-fluidic prism, its It is characterised by:The decay total reflection prism main body (1) is made up of silicon crystal or germanium crystal material, and the cover plate is by poly dimethyl Silicone compositions are made.
3. a kind of decay for detecting micro liquid Terahertz wave spectrum according to claim 1 is totally reflected micro-fluidic prism, its It is characterised by:The surface figure accuracy of the THz wave coupling surface (11) is less than 500nm, and surface roughness is less than 100nm, total reflection The incidence angle in face (12) is more than critical internal reflection angle.
4. a kind of decay for detecting micro liquid Terahertz wave spectrum according to claim 1 is totally reflected micro-fluidic prism, its It is characterised by:The area of the micro-channel structure (21) is more than Terahertz hot spot, the depth and evanescent wave of micro-channel structure (21) Penetration depth matches.
5. a kind of decay for detecting micro liquid Terahertz wave spectrum according to claim 2 is totally reflected micro-fluidic prism, its It is characterised by:The calculation formula of the critical internal reflection angle is as follows:
<mrow> <msub> <mi>sin&amp;theta;</mi> <mi>c</mi> </msub> <mo>=</mo> <mfrac> <msub> <mi>n</mi> <mrow> <mi>S</mi> <mi>o</mi> <mi>l</mi> </mrow> </msub> <msub> <mi>n</mi> <mi>c</mi> </msub> </mfrac> </mrow>
Wherein:θcFor critical internal reflection angle, nSolFor the refractive index of fluid sample, ncFor the refractive index of prism material of main part.
6. the preparation method of the micro-fluidic prism according to claim any one of 1-5, it is characterised in that:Include following step Suddenly:
S1:A burnishing surface for selecting silicon crystal or germanium crystal is fully reflecting surface;
S2:The incidence angle of wave beam coupling surface is designed, and THz wave coupling is made on crystal by cutting, wet etching, polishing Conjunction face, complete the making of decay total reflection prism main body;
S3:The planar graph of fluid channel is designed, and makes photo mask board;
S4:The male structure of fluid channel figure is made in substrate by photoetching process, the male template needed for injection is made;
S5:The prepolymer of dimethyl silicone polymer and crosslinking agent are well mixed, and polydimethylsiloxane liquid is uniformly filled After horizontal rest solidification, dimethyl silicone polymer piece is taken off from male template in male template for note;
S6:Through hole is made on dimethyl silicone polymer piece, completes the making of cover plate;
S7:By oxygen plasma bonding or thermal bonding method, by the decay total reflection prism main body in S2 and the cover plate in S6 It is brought into close contact, forms the flow passage structure of sealing.
7. the preparation method of micro-fluidic prism according to claim 6, it is characterised in that:In step S4, the male structure Height be 50-200 μm.
8. the preparation method of micro-fluidic prism according to claim 6, it is characterised in that:Male template is poured in step S5 On the thickness of dimethyl silicone polymer be 2-5mm.
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CN109060729A (en) * 2018-10-29 2018-12-21 中国人民解放军陆军军医大学第附属医院 Transwell detection device and method based on Terahertz Technique of Attenuated Total Reflectance
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