CN109470665A - A kind of method of fluorescence quantum detection glass surface and sub-surface damage - Google Patents
A kind of method of fluorescence quantum detection glass surface and sub-surface damage Download PDFInfo
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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Abstract
The invention discloses a kind of methods of fluorescence quantum detection glass surface and sub-surface damage, include the following steps: for CdSe/ZnS core-shell structure fluorescence quantum to be added in toluene, configuration concentration is the quantum dot toluene solution not less than 1mg/mL, it is mixed again with acetone by the volume ratio of (2:1)-(1:1), obtains quantum dot-toluene-acetone solution；Pit is ground in sample surfaces with steel ball by Ball-dimpling method and discloses sub-surface damage；Sample is immersed in quantum dot solution；Sample is placed under confocal microscope after organic solvent volatilization and is observed, fluorescence intensity change curve in the three-dimensional appearance and pit on surface is obtained；It is analyzed to obtain sample surfaces roughness with ImageJ software, the thickness of sub-surface damage layer is obtained according to fluorescence intensity change.The method of the present invention rapidly and accurately measures surface damage and sub-surface damage simultaneously, has good application prospect in optical device context of detection.
Description
Technical field
The present invention relates to a kind of detection method of glass material surface damage more particularly to a kind of sub-surface damage layer thickness
Detection method, for measuring a variety of glass materials such as optical element.This method can detect glass surface damage and sub- table simultaneously
Surface damage distribution situation quantitatively obtains the surface roughness and sub-surface damage layer thickness of glass material, ultraprecise may be implemented
The measurement of small sub-surface damage layer thickness caused by grinding.
Background technique
Measurement surface damage and the method for sub-surface damage have much at present, wherein surface damage with surface roughness come
It measures, the roughness of some glass is often measured with optical method, such as common scanning probe microscopy method, atomic force are aobvious
Micro mirror method, Interference Microscope Method, scattering method, speckle method, optics tracer method, diffraction approach etc..These optical methods measure surface damage
It is higher compared to traditional sample block comparison method accuracy, but it is partial to point-to-point measurement, reduce the efficiency of measurement.Sub-surface damage
The detection for hurting depth includes destructive detection method: HF chemical corrosion rate method, section microscopy, Ball Dimpling method etc., and
Nondestructive inspecting method: Magnetorheological Polishing spotting method, X-ray diffraction method, laser scattering method, total internal reflection intensity detection technology
Deng.Destructive method detection sub-surface damage is easy to operate, and intuitive is strong, it can be achieved that accurate quantification measures, but test specimen will receive damage；
Nondestructive inspecting method can guarantee the integrality on test block surface, but complicated mechanism, there are certain requirements to test sample, and right
Detecting instrument has biggish dependence.The above detection method cannot all measure to obtain the surface damage and Ya Biao of sample simultaneously
Surface damage, and for characterization that sub-surface damage can not be quantified in specific damage profile degree.
Quantum dot refers to the nano particle being made of in a manner a certain number of atoms, and three-dimensional dimension is between 1-
Between 10nm, unique physics and chemical property are shown, fluorescence can be emitted after being excited.Compared with organic fluorescence materials, tool
Have the advantages that spectrum it is narrow, exciting light spectrum width, optical stability is good and is not easy photobleaching, it is most important that, quantum dot energy band it is effective
Band gap can be reduced with the increase of particle size, can be realized the regulation to its photoelectric property by changing particle size, be made
It all has broad application prospects in fields such as biological medicine, information storage, solar battery, light emitting diodes.
Currently, quantum dot is applied to the sub-surface damage of detection glass material by existing research person, such as: document
W.Williams,B.Mullany,W.Parker,et al.Using quantum dots to evaluate subsurface
damage depths and formation mechanisms in glass[J].CIRP Annals-Manufacturing
Technology, 2010,59 (1): described in 569-572.It comprises the concrete steps that and quantum dot is added in grinding and polishing liquid, later with sharp
Light confocal fluorescent microscopic technology assesses the subsurface stratum damage of glass, and discovery quantum dot can be explicitly shown sub-surface damage
The position of wound.This method can only obtain the sub-surface damage distribution of sample, and quantitative characterization cannot be carried out to sub-surface damage,
And it cannot measure to obtain the surface damage of sample simultaneously.
Summary of the invention
The present invention proposes quick one kind, effective, accurate detection and observation glass aiming at the problem that background technique proposes
The method of the distribution and depth of surface damage and sub-surface damage.This method is detected in the surface damage and sub-surface damage of glass
Aspect has good actual application prospect.
The present invention is achieved by the following technical solutions:
A kind of method of fluorescence quantum detection glass surface and sub-surface damage, which is characterized in that described includes following
Step:
(1) quantum dot-toluene-acetone mixed solution is prepared:
S1. the fluorescence quantum of CdSe/ZnS core-shell structure is added in toluene, ultrasound makes to be uniformly dissolved, and configuration concentration is
Quantum dot toluene solution not less than 1mg/mL；
S2. by the obtained quantum dot toluene solution of step (1) S1 and acetone by quantum dot toluene solution: acetone=(2:1)-
The volume ratio of (1:1) mixes, and ultrasonic mixing uniformly obtains quantum dot-toluene-acetone solution；
(2) sample sub-surface damage layer is disclosed:
S3. the HF solution that configuration quality score is 10%；
S4. acquired solution in step (2) S3 is coated in glass sample surface 25-35s；
S5. pit, steel ball half is ground in the obtained sample surfaces steel ball of step (2) S4 and diamond paste cooperation
Diameter is R；
(3) it coats quantum dot: step (2) S4 sample handled is immersed in the resulting quantum dot-of step (1) S2.
3-5min in toluene-acetone solution, and it is dried to toluene and acetone is evaporated completely；
(4) detection of sample surfaces damage and sub-surface damage:
S6. the sample that step (3) processing obtains is placed under laser confocal microscope, excitation wavelength 405nm, observation
Pit and pit obtain sample surfaces damage and sub-surface damage distribution situation, measurement with exterior domain light field and fluorescent dark field
Pit diameter D；
S7. being continuously shot Z-direction picture and being superimposed can be obtained sample surfaces three-dimensional appearance figure；
(5) ImageJ software analysis surface roughness and sub-surface damage layer thickness: step (4) S7. is shot
Pit is opened with ImageJ software with the three-dimensional appearance figure of exterior domain and is analyzed, and sample surfaces roughness is obtained；Step (4) S6 is clapped
The fluorescence picture ImageJ software taken the photograph opens bracing wire measurement fluorescence intensity change curve, according to laser confocal microscope to recessed
The dark field fluorescent image of shooting is cheated, selection region measures fluorescence by the Plot Profile tool scribe line of ImageJ software
Gray value, obtaining sub-surface damage region to the pit edge i.e. horizontal distance on sample surface layer according to the strong and weak measurement of peak value is d,
And obtain thickness SSD=(d (D-d))/2R of sub-surface damage layer.
In the above-mentioned technical solutions, the CdSe/ZnS fluorescence quantum of the core-shell structure is the preparation of micro- reaction synthesis method
, include the following steps:
1, the synthesis of CdSe presoma
Configure cationic presoma and anion presoma:
Cationic presoma: 6.42mg chromium oxide powder and 0.5g trioctylphosphine are weighed in flask, 1.5mL oil is added
Amine, the oleic acid of 0.1mL and 2.4mL octadecylene, then place it in stirring under the oil bath environment that temperature is 150 DEG C and be not less than 1h to obtain
Obtain clear solution；
Anion presoma: weighing the selenium powder (Se) of 39.5mg in flask, be added 1.5mL oleyl amine, 1mL tri-n-octyl phosphine and
1.5mL octadecylene, magnetic agitation are not less than 1h；
Cation is extracted respectively with two syringes and anion precursor solution is placed on micro-injection pump, coutroi velocity
It for~30mL/h, is mixed by three-way device and magnetic stirring apparatus, solution is~70cm polytetrafluoroethylene (PTFE) hair by pipe range
Tubule is placed in 285 DEG C of oil baths and reacts to obtain CdSe presoma；
2, the package of ZnS: ZnS presoma: weighing 1.082g zinc diethyl dithiocarbamate in flask, is added
3mL tri-n-octyl phosphine, the octadecylene of 2mL and 3mL oleyl amine stir no less than 20min at room temperature and obtain clear solution；Pass through two
Syringe extracts CdSe precursor solution and the precursor solution of ZnS respectively, is placed on micro-injection pump, coutroi velocity be~
10mL/h, pipe range are~140cm, and reaction temperature is 140 DEG C, finally obtain the CdSe/ZnS quantum dot wrapped.
In the above-mentioned technical solutions, step (2) S5, diamond paste used are 10000 mesh.
In the above-mentioned technical solutions, in the step (5), the analysis of sample surfaces roughness is measured specifically: according to step
Suddenly (4) S7, the three-dimensional surface shape that sample is superimposed in the picture that Z-direction is continuously shot with laser confocal microscope
Figure, by the SurfCharJ plug-in unit of ImageJ software, analysis obtains the surface roughness value in surveyed region.
Beneficial effect
1, the present invention is based on surface damage and sub-surface damage of the fluorescence quantum to glass to detect, and energy is quick, has
Effect, accurate detection go out the size of sample surfaces roughness and the distribution of sub-surface damage and depth, this is current other surveys
Amount device cannot be accomplished, and be able to satisfy surface damage and the high-precision requirement of sub-surface damage measurement of optical element.
2, using method of the invention, surface damage and sub-surface damage in addition to being suitable for measuring glass are also used
In the surface damage and sub-surface damage that measure other fragile materials.
Detailed description of the invention
Fig. 1 is to grind the structural schematic diagram of pit in grinding optical glass surface in case study on implementation of the present invention,
Wherein, 1: universal joint, 2: steel ball, 3: the stainless steel mould of stationary balls and glass specimen, 4: glass specimen；
Fig. 2 is the three-dimensional appearance figure of surface damage in case study on implementation of the present invention；
Fig. 3 is the surface roughness value that ImageJ is analyzed in case study on implementation of the present invention；
Fig. 4 is pit areas phosphor pattern captured by Laser Scanning Confocal Microscope in case study on implementation of the present invention；
Fig. 5 is sub-surface damage area fluorescence intensity change curve in case study on implementation of the present invention；
Specific embodiment
Below in conjunction with Figure of description and specific implementation example, explanation is further described to the present invention, but be not intended to limit this
The protection scope of patent of invention.
Embodiment 1 weighs 15mg CdSe/ZnS nuclear shell structure quantum point and is dissolved in 15mL toluene, and ultrasound makes to be uniformly dissolved
To quantum dot toluene solution, 15mL acetone is added, ultrasonic mixing uniformly obtains quantum dot-toluene-acetone solution；
The HF solution that configuration quality score is 10%, is dipped with cotton swab and is coated in glass sample surface 30s, be 6mm with radius R
Steel ball and 10000 mesh diamond paste in sample surfaces with pit is ground, grinding device schematic diagram as shown in Figure 1,
It is immersed in quantum dot-toluene-acetone solution and is taken out after 3min again, be dried to toluene and acetone volatilization is complete；
The sample for being coated with quantum dot is placed under laser confocal microscope, setting excitation wavelength is 405nm, observes pit
And pit measures D=469.643 μm of pit diameter with exterior domain light field and fluorescent dark field, obtains sample surfaces damage and Asia
Surface damage distribution situation；
Laser confocal microscope, which is continuously shot Z-direction picture and is superimposed, can be obtained sample surfaces three-dimensional appearance figure, such as Fig. 2
It is shown；
ImageJ software analysis surface roughness and sub-surface damage layer thickness: laser confocal microscope is shot to obtain
Pit with the three-dimensional appearance figure of exterior domain with ImageJ software SurfCharJ plug-in unit analyze, the region samples surface can be obtained
Roughness, as shown in Figure 3；The fluorescence picture (Fig. 4) that laser confocal microscope is shot, with ImageJ software Plot
Profile function bracing wire measures fluorescence intensity change curve, quickly precise measurement can obtain sub-surface damage region to pit side
Edge, that is, sample surface layer horizontal distance is d, and thickness SSD=(d (D-d))/2R=2.809 of sub-surface damage layer is calculated
μm。
Claims (3)
1. a kind of method of fluorescence quantum detection glass surface and sub-surface damage, which is characterized in that described includes following step
It is rapid:
(1) quantum dot-toluene-acetone mixed solution is prepared:
S1. the fluorescence quantum of CdSe/ZnS core-shell structure is added in toluene, ultrasound makes to be uniformly dissolved, and configuration concentration is not small
In the quantum dot toluene solution of 1mg/mL；
S2. by the obtained quantum dot toluene solution of step (1) S1 and acetone by quantum dot toluene solution: acetone=(2:1)-(1:
1) volume ratio mixing, ultrasonic mixing uniformly obtain quantum dot-toluene-acetone solution；
(2) sample sub-surface damage layer is disclosed:
S3. the HF solution that configuration quality score is 10%；
S4. acquired solution in step (2) S3 is coated in glass sample surface 25-35s；
S5. pit is ground in the obtained sample surfaces steel ball of step (2) S4 and diamond paste cooperation, steel ball radius is
R；
(3) it coats quantum dot: step (2) S4 sample handled is immersed in the resulting quantum dot-toluene-of step (1) S2.
3-5min in acetone soln, and it is dried to toluene and acetone is evaporated completely；
(4) detection of sample surfaces damage and sub-surface damage:
S6. the sample that step (3) processing obtains is placed under laser confocal microscope, excitation wavelength 405nm observes pit
And pit is obtained sample surfaces damage and sub-surface damage distribution situation, is measured pit with exterior domain light field and fluorescent dark field
Diameter D；
S7. it is continuously shot Z-direction picture and is superimposed and obtain sample surfaces three-dimensional appearance figure；
(5) ImageJ software analysis surface roughness and sub-surface damage layer thickness: the pit that step (4) S7 is shot with
The sample surfaces three-dimensional appearance figure of exterior domain is opened with ImageJ software and is analyzed, and sample surfaces roughness is obtained；By step (4) S6
The fluorescence picture of shooting opens bracing wire with ImageJ software and measures fluorescence intensity change curve, according to laser confocal microscope pair
The dark field fluorescent image of pit shooting, selection region measure fluorescence by the Plot Profile tool scribe line of ImageJ software
Gray value, obtaining sub-surface damage region to the horizontal distance on the i.e. sample surface layer of pit edge according to the strong and weak measurement of peak value is
D, and obtain thickness SSD=(d (D-d))/2R of sub-surface damage layer.
2. the method for fluorescence quantum detection glass surface and sub-surface damage as described in claim 1, which is characterized in that institute
It states in step (2) S5, diamond paste used is 10000 mesh.
3. the method for fluorescence quantum detection glass surface and sub-surface damage as described in claim 1, which is characterized in that institute
It states in step (5), the analysis measurement of sample surfaces roughness specifically: according to step (4) S7, with laser confocal microscope pair
The three-dimensional surface shape figure that sample is superimposed in the picture that Z-direction is continuously shot, passes through the SurfCharJ of ImageJ software
Plug-in unit, analysis obtain the surface roughness value in surveyed region.
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| CN113607774A (en) * | 2021-07-15 | 2021-11-05 | 华东理工大学 | Electrode strain field in-situ monitoring device and method for marking fluorescent quantum dot speckles |
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