CN104020185B - A kind of assay method of macromolecule hyper-film phase transition temperature - Google Patents
A kind of assay method of macromolecule hyper-film phase transition temperature Download PDFInfo
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- CN104020185B CN104020185B CN201410274669.XA CN201410274669A CN104020185B CN 104020185 B CN104020185 B CN 104020185B CN 201410274669 A CN201410274669 A CN 201410274669A CN 104020185 B CN104020185 B CN 104020185B
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Abstract
The present invention relates to the assay method of a kind of macromolecule hyper-film phase transition temperature.Macromolecule hyper-film is plated in substrate by the present invention, use a branch of visible ray of pulsed and a branch of Infrared irradiation to the macromolecule hyper-film being plated in substrate, the optical signalling of a branch of detectable surface plasma will be launched owing to the optical nonlinearity of metallic substrates responds.Changing the disturbance to surface plasma signal intensity by measuring the structure of macromolecule hyper-film under different temperatures, i.e. can get the curve that signal intensity varies with temperature, this curve break is the phase transition temperature of corresponding macromolecule hyper-film.The method is measured simple, and accuracy is high, and favorable reproducibility, it is possible to achieve in site measurement has broad application prospects.
Description
Technical field
The present invention relates to the assay method of the nonlinear optics of a kind of macromolecule hyper-film phase transition temperature, belong to Materials testing and characterization field.
Technical background
Macromolecule hyper-film is widely used to industrial circle, as photoelectric device, permoselective membrane, protective coating and photoengraving etc.；The phase transition temperature of macromolecule membrane directly determines stability that thin film on device uses with ageing.Therefore, the phase transition temperature of size-constrained macromolecule hyper-film causes extensive concern and the discussion of domestic and international scientist.Start up to now from early 1990s, the phase in version of macromolecule hyper-film has had become as the focus of a research, various characterization methods the most progressively grow up, including ellipsometer test method, Brillouin light scattering method, neutron reflection method, fluorescent spectrometry, near side (ns) X-ray Absorption Fine Structure spectrometry, x-ray reflection method, scanning viscoelastic force microscope method, atomic force microscopy, calorimetry and lateral force microscopy method etc..
Detection method based on surface plasmon resonance effect exploitation has the methods such as Applications of surface plasmon resonance, surface enhanced raman spectroscopy, surface-reinforced infrared spectrum and surface-enhanced fluorescence spectrum.Applications of surface plasmon resonance is the quantity that the disturbance of a branch of light activated plasma signal realizes detecting binding molecule based on the molecule of absorption in substrate.Surface enhanced raman spectroscopy, surface-reinforced infrared spectrum and surface-enhanced fluorescence spectrum are the enhancings that transition based on detected intramolecular vibration level or electron energy level and substrate surface plasma generation resonance coupling effect realize detecting signal.Above detection technique all uses light beam to induce surface plasma signal.
Advantage of the invention is that and utilize second order nonlinear optical effect to produce surface plasma signal, i.e. a branch of visible ray and a branch of infrared light by pulsed produces surface plasma signal in the substrate plating a floor height molecular ultrathin films, and signal strength detection variation with temperature in the case of variations in temperature, when variations in temperature causes the phase in version of macromolecule hyper-film, the phase in version of macromolecule membrane will cause the unexpected transformation of plasma signal intensity, and the temperature that mensuration transition point corresponds to can measure the phase transition temperature of macromolecule hyper-film.
Summary of the invention
This patent discloses the assay method of a kind of macromolecule hyper-film phase transition temperature.The method induces second order nonlinear optical effect by the incident illumination of two pulses at the substrate surface plating a floor height molecular film, and produce the surface plasma signal under second-order effects, plasma signal is produced measurable disturbance by the phase in version of macromolecule hyper-film when the temperature is changed, the phase transition temperature of macromolecule hyper-film can be measured by measuring plasma signal intensity, this inventive method is simple, accuracy is high, is suitable for macromolecule scope wide.
Technical scheme is as follows:
A kind of assay method of macromolecule hyper-film phase transition temperature, it is characterised in that
Step one, the incident illumination of two pulses is radiated at the substrate surface being coated with macromolecule hyper-film, induces second order nonlinear optical effect, and produces the surface plasma signal under second-order effects；
Step 2, is stepped up the temperature of described substrate, gathers the plasma signal intensity of substrate surface；
Step 3, carries out linear fit by temperature and described plasma signal intensity, and the turning point of curve obtained is defined as the phase transition temperature of this ultrathin membrane.
The described substrate producing surface plasma nonlinear optical response, including metallic substrates and metal-oxide substrate etc..
Described macromolecule hyper-film is transparent for incident illumination and plasma signal, and is applicable to the macromolecule of various molecular weight and molecular weight distribution, such as polyethylene, polypropylene, polystyrene, Merlon and polyvinyl alcohol etc..
The incident illumination of described two pulses is respectively visible ray and infrared light；A length of 532 nanometers of described visible light wave, a length of 3226 nanometers of described infrared waves are to 3333 nanometers.
It is plated in suprabasil macromolecule hyper-film, uses rotary coating, solution to pour into a mould dry or LBL self-assembly and macromolecule hyper-film is plated in substrate by absorption.The thickness of described macromolecule hyper-film is that several nanometer includes glass transition temperature, secondary relaxation temperature and melt temperature to hundreds of nanometers, described phase transition temperature.
Beneficial effects of the present invention is as follows: the present invention compensate for existing calorimetry cannot measure the vacancy of Nano grade macromolecule hyper-film phase transition temperature.Present invention utilizes nonlinear optical effect, during measurement, do not damage the structure of macromolecule hyper-film, be a kind of novel high sensitivity Dynamic Non-Destruction Measurement, additionally this method is measured simple, and accuracy is high, favorable reproducibility, in site measurement can be realized, have broad application prospects.
Accompanying drawing explanation
Figure 1 Measure the experimental technique flow chart of macromolecule hyper-film phase transition temperature.
Figure 2 Plate the second-order surface plasma signal that the substrate of 20 nanometer thickness polymethyl methacrylate films produces under pulsed visible-light and infrared light.Pulsed visible-light wavelength is 532 nanometers, and pulsed infrared light frequency is set to from 3000 wave numbers to 3100 wave numbers (being that 3226 nanometers are to 3333 nanometers corresponding to wavelength), and one-shot measurement produces 20 data points.Measuring temperature is 292 K.
Figure 3It is coated with the plasma signal of gold substrate sample of four different-thickness polymethyl methacrylate films with the change curve of sample temperature.In figure, circle is experimental data point, and straight line is the result of piecewise fitting, and turning point is the phase transition temperature of the polymethyl methacrylate film of correspondence.
Figure 4 The phase transition temperature of three kinds of different polyphosphazene polymer methyl methacrylates (PMMA), polybenzyl methacrylate (PBMA) and polyethyl methacrylate (PEMA) thin film measured and the relation curve of film thickness.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
The present invention specifically comprises the following steps that
1. preparation produces the substrate of plasma signal.The preparation of substrate: the preparation of substrate is divided into following 3 steps: the cleaning of (1) sheet glass.First, the sheet glass of 1cm × 1cm is put into new preparation Piranha washing liquid (volume ratio be 3:1 98% concentrated sulphuric acid and the mixed solution of hydrogen peroxide of 30%) in soak more than 24 hours, the most ultrasonic 20 min, sheet glass is taken out, with distilled water ultrasonic cleaning 20 min, use distilled water flushing 3 times the most again, dry up stand-by；(2) on the sheet glass that (1) step cleans up, last layer nickel (about 10 nanometer) is plated with ion sputtering instrument in order to increase the adhesive property of glass sheet surface；(3) on nickel dam, the layer gold of about 500 nanometer thickness is sputtered with ion sputtering instrument.The substrate prepared puts into the exsiccator of sealing to avoid surface contamination.
2. the preparation of macromolecule hyper-film sample in substrate: macromolecule (polymethyl methacrylate, polyethyl methacrylate or polybenzyl methacrylate etc.) is dissolved in respective solvent, and it is configured to the solution from 0.1% to 2% mass ratio, being prepared in substrate by macromolecule hyper-film by rotary coating instrument, rotating speed controls at 1000 revs/min to 8000 revs/min.The thickness of thin film can be controlled in 1 nanometer to 500 nanometers by two conditions: the concentration of (1) solution；(2) rotating speed of rotary coating.Being plated in suprabasil macromolecule hyper-film to process 4 hours in vacuum drying oven interior-heat, temperature controls below measured phase transition temperature about 20 degrees Celsius.The thickness of film sample is recorded by ellipsometer test.
3. the generation of plasma signal and collection: the visible ray of pulse and infrared light are produced by the Peace Park instrument of commercial Aix-en-Provence agate company.The generation process of pulsed visible-light is as follows, Nd:YAG laser instrument produce the pulse fundamental frequency light that a branch of wavelength is 1064 nanometers, and frequency is 20 psecs, and partial pulse fundamental frequency light is by amplifying and the visible ray that process generation wavelength is 532 nanometers of frequency multiplication.The generation process of pulsed infrared light is as follows, the pulse fundamental frequency light that a branch of wavelength is 1064 nanometers is produced by Nd:YAG laser instrument, partial pulse fundamental frequency light is by amplifying and the ultraviolet light that process generation wavelength is 355 nanometers of frequency tripling, the process that the ultraviolet light of 355 nanometers and the fundamental frequency light of 1064 nanometers occur parametric oscillation under the effect of LBO nonlinear crystal, produce and amplify, obtaining wavelength from 1190 nanometers to the laser of 1980 nanometers, the fundamental frequency light of this Shu Jiguang and 1064 nanometers passes through AgGaS2Nonlinear crystal produces difference frequency, obtains required infrared light, and wavelength is that 2300 nanometers are to 10000 nanometers.Visible ray and the infrared light of pulse are directed on sample by optics, under the irradiation of two-beam, will produce nonlinear surface plasma signal, and the surface plasma signal of outgoing is collected by monochromator.The alternating temperature process of sample is controlled by the programmed temperature-rising controller CN7800 of omega engineering company, sample is placed on the warm table of programmed temperature-rising controller, temperature is set, minimum temperature sets at least to below transition temperature 20 degrees Celsius, maximum temperature is minimum is set to more than phase transition temperature 20 degrees Celsius, to ensure the reliability measured.Wait when surveyed sample temperature reaches set temperature, start to gather data.When gathering data, a length of 532 nanometers of visible light wave of pulse, the infrared band of pulse is set to 3226 nanometers to 3333 nanometers, and the plasma signal wave band of generation is that 457 nanometers are to 459 nanometers；The polarization direction of the plasma signal light of incident visible ray, infrared light and detection is all adjusted to P polarization；Data point at a temperature of each is at least three meansigma methodss measured.Making graph of relation with plasma signal strength versus temperature, the turning point on curve is i.e. corresponding to the phase transition temperature of macromolecule hyper-film.
As Fig. 1 shows the experimental technique flow chart of mensuration macromolecule hyper-film phase transition temperature.Laser instrument produces the basic frequency laser that a branch of wavelength is 1064 nanometers and pulse is 20 psecs, it is 532 nanometers and the laser of 355 nanometers that basic frequency laser produces wavelength by frequency multiplication and frequency tripling, the laser of 355 nanometers passes through LBO nonlinear crystal and attached device generation optical parametric oscillator, produces and amplify, obtaining a branch of wavelength is 1190 nanometers laser to 1980 nanometers, and the fundamental frequency light of this Shu Jiguang and 1064 nano wave lengths is at AgGaS2Difference frequency is there is under nonlinear crystal effect, producing wavelength is 3226 nanometers infrared lights to 3333 nanometers, wavelength is the visible ray of 532 nanometers and the infrared light that wavelength is 3226 nanometers to 3333 nanometers is directed on sample stage, the substrate sample of plating last layer 20 nanometer polymethyl methacrylate film overlaps, the angle of incidence of visible ray and infrared light is respectively 60 ° and 54 °, substrate sample surface occurs second nonlinear to respond under the effect of two-beam, surface plasmon oscillations will be produced, and launch a branch of flashlight, its angle of emergence is 59 °, and detected by monochromator.The temperature of sample is controlled by omega engineering company programmed temperature-rising controller, the temperature of sample rises with 5K interval, 367K is risen to from 292K, after temperature arrives design temperature balance 2 minutes, by monochromator collection surface plasma signal, gather 20 data points at each temperature, under 14 different temperatures, gather 280 data points altogether.Fig. 2 be under 292 K at iraser wave band from 3000 cm-1To 3100 cm-1In the range of (corresponding to the wavelength of 3226 nanometers to 3333 nanometers) measure the surface plasma signal that arrives.Repeated measure three times, the plasma signal intensity data measured at a temperature of each is averaged, with meansigma methods, temperature is made curve, obtain the data point as marked in Fig. 3 A with circle, data point carries out point two sections of linear fits, and the phase transition temperature obtaining the polymethyl methacrylate film that thickness is 20 nanometers is 319K.
Embodiment 2: plating thickness on the metallic substrate is 30 nanometers, 60 nanometers and the polymethyl methacrylate film of 107 nanometers, other is such as embodiment 1, as shown in Fig. 3 B, 3C and 3D.
Embodiment 3: plate the polymethyl methacrylate film (20 nanometers, 30 nanometers, 60 nanometers, 107 nanometers and 110 nanometers) of different-thickness, polybenzyl methacrylate thin film (26 nanometers, 27 nanometers, 34 nanometers, 45 nanometers and 56 nanometers) and polyethyl methacrylate thin film (17 nanometers, 44 nanometers, 70 nanometers and 125 nanometers) on the metallic substrate, other is such as embodiment 1, and film thickness is made curve chart, as shown in Figure 4 with the thin film phase transition temperature measured.
Claims (8)
1. the assay method of a macromolecule hyper-film phase transition temperature, it is characterised in that comprise the following steps:
Step one, the incident illumination of two pulses is radiated at the substrate surface being coated with macromolecule hyper-film, produces second order
Surface plasma signal under effect；
Step 2, is stepped up the temperature of described substrate surface, gathers the plasma signal intensity of substrate surface；
Step 3, carries out linear fit by temperature and described plasma signal intensity, the turning point of curve obtained
It is defined as the phase transition temperature of this ultrathin membrane.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 1, its feature exists
In, described substrate is the substrate with surface plasma nonlinear optical response.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 1, its feature exists
In, described macromolecule hyper-film is transparent for incident illumination and plasma signal.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 1, its feature exists
In, the incident illumination of described two pulses is respectively visible ray and infrared light.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 4, its feature exists
In, a length of 532 nanometers of described visible light wave, a length of 3226 nanometers of described infrared waves are to 3333 nanometers.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 1, its feature exists
In, it is plated in suprabasil macromolecule hyper-film, uses the cast of rotary coating, solution to be dried or LBL self-assembly
With absorption, macromolecule hyper-film is plated in substrate.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 1, its feature exists
In, the thickness of described macromolecule hyper-film is that several nanometer is to hundreds of nanometers.
The assay method of macromolecule hyper-film phase transition temperature the most according to claim 1, its feature exists
In, described phase transition temperature includes glass transition temperature, secondary relaxation temperature or melt temperature.
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