CN115141397B - Composite film, preparation method and application thereof - Google Patents
Composite film, preparation method and application thereof Download PDFInfo
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- CN115141397B CN115141397B CN202210946363.9A CN202210946363A CN115141397B CN 115141397 B CN115141397 B CN 115141397B CN 202210946363 A CN202210946363 A CN 202210946363A CN 115141397 B CN115141397 B CN 115141397B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/04—Oxygen-containing compounds
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- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
Abstract
The invention discloses an eosin Y/zinc phthalocyanine composite PVA film, wherein eosin Y has strong saturated absorption and zinc phthalocyanine has strong reverse saturated absorption. The absorption characteristic changes along with the mass fraction change between substances, the transmittance can be regulated and controlled by adjusting the mass fraction proportion, and the nonlinear absorption coefficient of the material is adjusted, so that the composite material simultaneously has two properties of saturated absorption and reverse saturated absorption, and further, the nonlinear absorption property of the obtained composite film material can be freely adjusted.
Description
Technical Field
The invention belongs to the field of optical materials, and particularly relates to a novel composite film with freely adjustable nonlinear absorption coefficient
Background
The strong laser can cause permanent damage to human eyes and light sensors, and along with the development and application of the laser, people are prompted to seek effective protection means, and a novel optical limiter is developed. Because of special molecular and energy level structures, the existing optical material has nonlinear absorption property, and refractive index and absorption coefficient change along with light intensity, so that the phase, amplitude, polarization, transmission direction and the like of radiated light are changed, and the optical material can be used for manufacturing optical switches, logic gates, optical signal processors and the like, and has important application value in the fields of laser, communication, photoelectric instruments and the like.
The existing optical composite film has only single saturated absorption or anti-saturated absorption characteristic, and it is necessary to propose an optical composite film which simultaneously shows the saturated absorption and anti-saturated absorption characteristics according to practical requirements.
Disclosure of Invention
The invention provides a novel composite film with a freely adjustable nonlinear absorption coefficient, which realizes the adjusting function between saturated absorption and reverse saturated absorption, and simultaneously, firstly proposes to prepare a composite film by using polyvinyl alcohol, eosin Y and zinc phthalocyanine.
The technical scheme for solving the problems is as follows:
a composite film, comprising: polyvinyl alcohol, a saturated absorbing material and a reverse saturated absorbing material, wherein the saturated absorbing material is eosin Y; the reverse saturation absorbing material is zinc phthalocyanine.
PVA is utilized to have no nonlinear absorption, the absorption characteristics of eosin Y and zinc phthalocyanine are not affected, and PVA only provides a good dispersing film forming environment. Furthermore, the eosin Y has small light transmittance and large absorption, and the eosin Y has large light transmittance and small absorption. The phthalocyanine zinc has small transmittance near the focal point and has large transmittance when reverse saturation absorption is not excited at a position far away from the focal point.
The composite film has good absorption under low light intensity and high light intensity, and the transmittance is limited in a certain range.
The preparation method of the composite film solution comprises the following steps of:
1.5-3.0 parts of eosin Y; 5000 parts of polyvinyl alcohol; 45-65 parts of zinc phthalocyanine; 100000 portions of deionized water;
preferably, the composite film solution has eosin Y of 0.015-0.03g; 50g of polyvinyl alcohol; 0.45-0.65g of zinc phthalocyanine; 1000g of deionized water.
Preferably, the method comprises the following steps of:
eosin Y1.5 parts; 5000 parts of polyvinyl alcohol; 65 parts of zinc phthalocyanine; 100000 portions of deionized water.
In order to obtain a novel composite film with the nonlinear absorption coefficient capable of being freely adjusted, the invention also provides a preparation method of the composite film, which comprises the following steps:
s1, preparing PVA solution with mass fraction of 5%;
s2, adding a certain amount of eosin Y and zinc phthalocyanine into the PVA solution obtained in the step S1;
s3, stirring the mixed solution obtained in the step S2 for 1 hour by using a magnetic stirrer at the constant temperature of 45 ℃, stirring the mixed solution obtained in the step S2 by using ultrasonic waves with the frequency of 20kHz and the power of 20kW for 20 minutes, cooling for 10 minutes, and stirring for 2 hours at the frequency to obtain a uniformly mixed eosin Y/zinc phthalocyanine composite PVA solution, wherein the particle size of the zinc phthalocyanine after ultrasonic treatment is smaller and more uniform; controlling the size of zinc phthalocyanine particles to be in a nano level, wherein the particles are wrapped among PVA molecules of a matrix;
s4, respectively taking 10mL of uniform eosin Y/zinc phthalocyanine compound PVA solution, casting the solution onto a clean glass substrate with the thickness of 9cm multiplied by 12cm, and horizontally placing the glass substrate in a clean darkroom for 4-5 days to obtain the eosin Y/zinc phthalocyanine compound PVA film.
According to the characteristics of the composite membrane, a method for adjusting the nonlinear absorption coefficient of the composite membrane is also provided,
obtaining polyvinyl alcohol and zinc phthalocyanine solution;
maintaining the zinc phthalocyanine concentration unchanged;
adding a suitable amount of eosin Y to the polyvinyl alcohol and zinc phthalocyanine solution;
the nonlinear absorption coefficient was adjusted as the concentration of eosin Y in the solution was varied.
Further, the novel composite film with the nonlinear absorption coefficient capable of being freely adjusted is used for manufacturing novel optical switches, limiters and mode lockers.
The invention has the beneficial effects that: it is realized that one material has two properties at the same time, and has saturated absorption and reverse saturated absorption. Further material non-linear properties can be tuned.
Drawings
FIG. 1 is a photograph of composite film FH3 object and SEM, wherein, (a) composite film FH3 object; (b) composite film FH3 SEM picture;
FIG. 2 is the UV-visible absorption spectra of film PVA, EY/PVA, znPc/PVA, FH2, FH4;
FIG. 3 is an open-cell Z-scan experimental setup and principle;
FIG. 4 is an open cell Z-scan graph in which (a) a polyvinyl alcohol (PVA) film; (b) different concentrations of eosin Y/PVA film;
FIG. 5 is an open pore Z scan curve of zinc phthalocyanine/PVA films of different concentrations;
FIG. 6 is an open cell Z scan curve of a different concentration eosin Y/zinc phthalocyanine composite PVA film, wherein (a) (b) composite film FH1; (c) (d) composite film FH2; (e) (f) composite film FH3; (g) (h) a composite film FH4;
FIG. 7 is a graph showing the normalized transmittance versus incident light intensity of eosin Y/zinc phthalocyanine composite PVA film FH3, FH4, 0.65g.L-1 zinc phthalocyanine/PVA film.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Examples
As shown in fig. 1, a composite film comprising: polyvinyl alcohol, a saturated absorbing material and a reverse saturated absorbing material, wherein the saturated absorbing material is eosin Y; the reverse saturation absorbing material is zinc phthalocyanine. The left part of the figure 1 (a) is an eosin Y/zinc phthalocyanine composite PVA film entity, and the right part of the figure 1 (a) is a control clean substrate. Fig. 1 (b) is an SEM photograph of the film, showing that zinc phthalocyanine particles are nano-sized, and the particles are encapsulated between PVA molecules of the matrix.
As shown in FIG. 2, the PVA film had no distinct characteristic absorption peak, and the eosin Y/PVA film exhibited a sharp absorption peak around 528 nm. The zinc phthalocyanine/PVA film exhibits an absorption valley around 519nm, exhibits a weak linear absorption around 532nm as the light source wavelength in the text, and has a weak absorption peak around 678nm as the Q-band. The composite films FH2 and FH4 both show characteristic absorption peaks near 528nm and 678nm, and no other characteristic peaks appear, which indicates that the composite film is a physical combination of eosin Y and zinc phthalocyanine and has absorption characteristics of eosin Y and zinc phthalocyanine.
The preparation method of the composite film comprises the following steps:
s1, preparing PVA solution with mass fraction of 5%;
s2, adding a certain amount of eosin Y and zinc phthalocyanine into the PVA solution obtained in the step S1;
s3, stirring the mixed solution obtained in the step S2 for 1 hour by using a magnetic stirrer at the constant temperature of 45 ℃, stirring the mixed solution obtained in the step S2 by using ultrasonic waves with the frequency of 20kHz and the power of 20kW for 20 minutes, cooling for 10 minutes, and stirring for 2 hours at the frequency to obtain a uniformly mixed eosin Y/zinc phthalocyanine composite PVA solution, wherein the particle size of the zinc phthalocyanine after ultrasonic treatment is smaller and more uniform; controlling the size of zinc phthalocyanine particles to be in a nano level, wherein the particles are wrapped among PVA molecules of a matrix;
s4, respectively taking 10mL of uniform eosin Y/zinc phthalocyanine compound PVA solution, casting the solution onto a clean glass substrate with the thickness of 9cm multiplied by 12cm, and horizontally placing the glass substrate in a clean darkroom for 4-5 days to obtain the eosin Y/zinc phthalocyanine compound PVA film.
Experimental example
(one) preparing a sample
Selecting materials:
1. eosin Y (EY) molecular weight 691.85, a dye that is reductive and poorly photolytic, is highly photoinitiating and is often used in photoinitiating systems. The molecule has a singlet state-triplet state energy level structure, the probability of transition from the singlet state to the triplet state is large, the absorption spectrum is wide, the linear absorption peak is 528.7nm, and the absorption section is 10 -16 cm 2 Magnitude of magnitude;
2. the molecular weight of zinc phthalocyanine (ZnPc) is 577.91, and the periphery of the molecule has no substituent. The zinc phthalocyanine molecule is of a five-level structure, the light energy absorbed by the molecule transits to two singlet excited states from a ground state, the singlet excited states cross to a triplet excited state through a system, the number of molecules is accumulated in the long-life triplet excited state, and then the molecule transits to a high-level triplet excited state, so that the absorption of strong radiation light is realized;
3. polyvinyl alcohol (PVA) is a polyhydroxy polymer having excellent physical and chemical properties such as high water solubility, high light transmittance, good stability, good film forming property, etc., and is widely used in industrial, medical and biological fields. The degree of polymerization is varied, and the molecular weight is several thousands to hundreds of thousands, and different molecular weights affect the dispersity of the nanoparticles. Polyvinyl alcohol is used as the film substrate.
The eosin Y/PVA film was prepared as follows:
s1, preparing PVA solution with mass fraction of 5%;
s2, adding a certain amount of eosin Y into the PVA solution obtained in the step S1;
s3, stirring the mixed solution obtained in the step S2 for 1 hour by using a magnetic stirrer at the constant temperature of 45 ℃ to obtain a uniform eosin Y/PVA solution;
s4, respectively taking 10mL of uniform eosin Y/PVA solution, casting the solution onto a clean glass substrate with the thickness of 9cm multiplied by 12cm, and horizontally placing the glass substrate in a clean darkroom for 4-5 days to obtain the eosin Y/PVA film.
The procedure for the preparation of zinc phthalocyanine/PVA film is as follows:
s1, preparing PVA solution with mass fraction of 5%;
s2, adding a certain amount of zinc phthalocyanine into the PVA solution obtained in the step S1;
s3, stirring the mixed solution obtained in the step S2 at room temperature by adopting ultrasonic waves with the frequency of 20kHz and the power of 20kW for 20 minutes, cooling for 10 minutes, and stirring for 2 hours at the frequency to obtain a uniformly mixed zinc phthalocyanine/PVA solution, wherein the size of zinc phthalocyanine particles after ultrasonic treatment is smaller and more uniform;
s4, taking 10mL of uniform and uniform zinc phthalocyanine/PVA solution, casting the solution onto a clean glass substrate with the thickness of 9cm multiplied by 12cm, and horizontally placing the glass substrate in a clean darkroom for 4-5 days to obtain the zinc phthalocyanine/PVA film.
The preparation of the eosin Y/zinc phthalocyanine composite PVA film comprises the following steps:
s1, preparing PVA solution with mass fraction of 5%;
s2, adding a certain amount of eosin Y and zinc phthalocyanine into the PVA solution obtained in the step S1;
s3, stirring the mixed solution obtained in the step S2 for 1 hour by using a magnetic stirrer at the constant temperature of 45 ℃, stirring the mixed solution obtained in the step S2 by using ultrasonic waves with the frequency of 20kHz and the power of 20kW for 20 minutes, cooling for 10 minutes, and stirring for 2 hours at the frequency to obtain a uniformly mixed eosin Y/zinc phthalocyanine composite PVA solution, wherein the particle size of the zinc phthalocyanine after ultrasonic treatment is smaller and more uniform;
s4, respectively taking 10mL of uniform eosin Y/zinc phthalocyanine compound PVA solution, casting the solution onto a clean glass substrate with the thickness of 9cm multiplied by 12cm, and horizontally placing the glass substrate in a clean darkroom for 4-5 days to obtain the eosin Y/zinc phthalocyanine compound PVA film.
Samples of eosin Y/PVA film (EY/PVA), zinc phthalocyanine/PVA film (ZnPc/PVA) and eosin Y/zinc phthalocyanine composite PVA Film (FH) were obtained, which were FH1 to FH4 according to the different numbers of the individual material components.
Taking different concentrations of eosin Y/PVA film (EY/PVA) solution, preparing film samples with evenly dispersed nano particles and flat surface by using a solution casting method,
wherein, the concentration is respectively: 1.5X10 -2 g·L -1 ，3.0×10 -2 g·L -1 ，4.5×10 -2 g·L -1 。
Taking different zinc phthalocyanine/PVA film (ZnPc/PVA) solution concentrations, preparing a film sample with uniformly dispersed nano particles and smooth surface by a solution casting method,
wherein, the concentration is respectively: 0.45 g.L -1 ，0.65g·L -1 。
Taking different concentrations of eosin Y/zinc phthalocyanine composite PVA Film (FH) solution, preparing a film sample with uniformly dispersed nano particles and smooth surface by a solution casting method, wherein,
eosin Y/zinc phthalocyanine composite PVA film FH1: the concentration of zinc phthalocyanine is 0.45 g.L -1 The concentration of eosin Y was 1.5X10 -2 g·L -1 ；
Eosin Y/zinc phthalocyanine composite PVA film FH2: the concentration of zinc phthalocyanine is 0.45 g.L -1 The concentration of eosin Y was 3.0X10 -2 g·L -1 ；
Eosin Y/zinc phthalocyanine composite PVA film FH3: phthaleinThe concentration of the cyanine zinc is 0.65 g.L -1 The concentration of eosin Y was 1.5X10 -2 g·L -1 ；
Eosin Y/zinc phthalocyanine composite PVA film FH4: the concentration of zinc phthalocyanine is 0.65 g.L -1 The concentration of eosin Y was 3.0X10 -2 g·L -1 。
(II) selection experiment method and device
The nonlinear refractive index and absorption coefficient are important parameters that characterize the nonlinear optical properties of a material. The Z scanning method is a simple and sensitive method for measuring the nonlinear optical property of the material compared with a nonlinear interferometry method, a degenerate four-wave mixing method and the like, and can measure the numerical value and positive and negative of the nonlinear refractive index and the absorption coefficient of the material by using a single light beam. The nonlinear refractive index is measured under closed cells and the nonlinear absorption coefficient is measured under open cells.
The nonlinear absorption characteristics of eosin Y/PVA film (EY/PVA), zinc phthalocyanine/PVA film (ZnPc/PVA) and eosin Y/zinc phthalocyanine composite PVA Film (FH) samples were studied using the open-cell Z scanning device shown in fig. 3.
Single PVA film, eosin Y/PVA film and zinc phthalocyanine/PVA film experimental comparison
By using the relation between the absorption coefficient of the material and the incident light intensity
α＝α 0 +βI (1)
Wherein: alpha 0 Is the linear absorption coefficient at low light intensity, beta is the nonlinear absorption coefficient, and I is the light intensity. The nonlinear absorption type determines the relation between beta and light intensity, beta can change positive and negative along with the increase of the light intensity, and different relations can be shown under different wavelengths.
Taking z=0 at the focal point of the positive lens L, and the relation between the normalized transmittance and z is that
Wherein: q 0 (z)＝βI 0 L eff /[1+(z/z 0 ) 2 ]，
For the light intensity at the focus, E 0 For pulse energy, τ is pulse width, equivalent thickness L eff ＝[1-exp(-α 0 l)]/α 0 Linear absorption coefficient alpha 0 = -ln (T)/l, l=40 μm is film thickness, rayleigh length +.>
ω 0 Is the girdle radius. Imaginary part Im chi of third-order nonlinear polarization rate (3) The relation of the nonlinear absorption coefficient beta is that
Wherein: epsilon 0 、c、n 0 Vacuum dielectric constant, light velocity and sample linear refractive index respectively.
As shown in fig. 4, an open-cell Z-scan plot in which (a) a polyvinyl alcohol (PVA) film; (b) The Z scan curves of the pure polyvinyl alcohol films measured with the apparatus shown in fig. 3 for the different concentrations of eosin Y/PVA film are shown in fig. 4 (a) with no nonlinear absorption effect of polyvinyl alcohol. A PVA solution of eosin Y was prepared and a solution casting process was used to prepare the eosin Y/PVA film. The Z-scan curve of the eosin Y/PVA film measured using the apparatus of FIG. 3 is shown in FIG. 4 (b). The absorption coefficient decreases with increasing light intensity and the optical absorption decreases, as the material is "bleached". Eosin Y is stable in nature and absorption coefficient is stable by repeated measurements. The eosin Y can excite saturated absorption under low light intensity, and the low light intensity has larger absorption coefficient and high molar absorption coefficient, thus indicating that the eosin Y has better photoinitiation efficiency. The high mass fraction film has strong saturated absorption. The experimental data of the three samples were fitted separately using equation (2) to obtain the corresponding parameters as shown in table 1.
As shown in FIG. 5, the open pore Z scanning curves of the zinc phthalocyanine/PVA film with different concentrations are prepared, the PVA solution of the zinc phthalocyanine is prepared, and the zinc phthalocyanine/PVA film is prepared by solution casting. The Z-scan curve of the zinc phthalocyanine/PVA film measured by the apparatus of FIG. 3 is shown in FIG. 5. Under nanosecond pulse laser, the curve is in a single valley characteristic, which shows that the zinc phthalocyanine/PVA film has reverse saturation absorption, and the nonlinear absorption coefficient beta is positive. The excited state absorption cross section of the zinc phthalocyanine is 3.2 times that of the ground state absorption cross section, so that the zinc phthalocyanine generates reverse saturation absorption. Almost transparent in weak light and absorption increased in strong light, the material is like "blackened". The experimental data of the two samples were fitted separately using equation (2) to give the parameters shown in table 1.
Table 1 parameters of eosin Y and zinc phthalocyanine film
It can be seen that under pulsed laser action, Z-scan shows eosin Y to have saturated absorption characteristics with nonlinear absorption coefficient β increasing with mass fraction. The zinc phthalocyanine has reverse saturation absorption characteristics, the nonlinear absorption coefficient beta is increased along with the increase of the mass fraction, and the stability of the zinc phthalocyanine and the nonlinear absorption coefficient beta is good.
Eosin Y/zinc phthalocyanine composite PVA film experiment
When nonlinear absorption of opposite signs occurs simultaneously on materials, the total absorption coefficient is
Wherein: alpha 0 /(1+I/I s ) Beta I is the effect of anti-saturation absorption, I s Is the saturated intensity.
Normalized transmittance when perforated is
Wherein: alpha (I) is shown as a formula (4), and beta and I can be obtained by fitting transmittance experimental data with a formula (5) s Numerical values.
As shown in table 2, four concentrations of eosin Y/zinc phthalocyanine composite PVA film, among them,
FH1: the concentration of zinc phthalocyanine is 0.45 g.L -1 The concentration of eosin Y was 1.5X10 -2 g·L -1 ；
FH2: the concentration of zinc phthalocyanine is 0.45 g.L -1 The concentration of eosin Y was 3.0X10 -2 g·L -1 ；
FH3: the concentration of zinc phthalocyanine is 0.65 g.L -1 The concentration of eosin Y was 1.5X10 -2 g·L -1 ；
FH4: the concentration of zinc phthalocyanine is 0.65 g.L -1 The concentration of eosin Y was 3.0X10 -2 g·L -1 。
At two light intensities I 0 The Z scan curves of the four films measured using the apparatus of fig. 3 are shown in fig. 6, the squares are experimental data, the solid lines are curves fitted according to the formulas (4), (5), the four samples all exhibit nonlinear absorption, and the parameters obtained by fitting are shown in table 2. When I 0 9.40GW cm -2 And in addition, the transmittance of the four samples is smaller at the weak light intensity far from the focus.
The light intensity is gradually increased from the focus of positive and negative directions, the transmittance is increased and then reduced, the transmittance reaches minimum at the focus, and the Z scanning curve shows the characteristic of M top. There is a mechanism to shift from saturated to reverse saturated absorption, which is shown as saturated absorption away from the focal point and stronger reverse saturated absorption near the focal point. When I 0 6.11GW cm -2 At this time, no significant anti-saturation absorption was observed for sample FH2, showing only saturation absorption of eosin Y. Experimental data were not completely symmetrical about the focus, probably due to thermal effects induced by using successive pulses at 10 Hz.
TABLE 2 composition of composite materials
As shown in fig. 6, the open pore Z scan curve of the eosin Y/zinc phthalocyanine composite PVA film. (a) (b) a composite film FH1; (c) (d) composite film FH2; (e) (f) composite film FH3; (g) (h) a composite film FH4;
since PVA does not have nonlinear absorption, as shown in fig. 4 (a), does not affect the absorption characteristics of eosin Y and zinc phthalocyanine, and further PVA only provides a good dispersed film forming environment. Further, as shown in fig. 6, the nonlinearity of eosin Y and zinc phthalocyanine can be expressed alone without eliminating each other's absorption characteristics. The composite material has both saturated absorption and reverse saturated absorption.
When the mass fraction of zinc phthalocyanine is the same, the top valley becomes shallow, the reverse saturation absorption is inhibited or even completely inhibited, and only the saturated absorption is shown, so that the saturated absorption in the ground state has the advantage of preferential excitation.
When the mass fraction of eosin Y is the same, the top valley is deep, the reverse saturation absorption is enhanced, and the reverse saturation absorption of the excited state is dominant under high light intensity.
As shown in fig. 7, the transmittance of the zinc phthalocyanine/PVA film gradually decreases with increasing light intensity, exhibiting optical clipping behavior. The transmittance of the composite films FH3 and FH4 increases with the increase of the light intensity under low light intensity, and the composite films are saturated absorption. At high light intensity, the transmittance is reduced, and the light is absorbed in reverse saturation, so that the light limiting action is realized. The composite film is changed from saturation absorption to reverse saturation absorption, a converted light intensity threshold exists, and the converted light intensity threshold can be regulated and controlled by doping of eosin Y. When the light intensity does not reach the threshold light intensity of the material, the material shows saturation absorption of eosin Y, and when the light intensity is higher than the threshold light intensity of the material, the material shows anti-saturation absorption of zinc phthalocyanine. This unique behavior can be used for passive laser mode locking and optical clipping.
When the concentration of zinc phthalocyanine is the same as shown in table 2, different nonlinear absorption coefficients beta can be obtained by changing the concentration of eosin Y, and a proper amount of saturated absorption material is doped in the anti-saturated absorption material, so that the nonlinear absorption coefficient beta can be continuously adjusted, the purpose of effectively controlling the output light intensity is achieved, and the optical limiter can be used for novel optical limiters and optical switches.
By the above-mentioned experiment, the composition,
the nonlinear absorption characteristics of eosin Y, zinc phthalocyanine, and eosin Y/zinc phthalocyanine composite films were studied using the Z scanning technique. Under the action of laser with pulse energy of 130 mu J, pulse width of 4ns and wavelength of 532nm, eosin Y has strong saturated absorption, zinc phthalocyanine has strong reverse saturated absorption, absorption characteristics are enhanced along with the increase of mass fraction, and repeated tests show that the eosin Y and the zinc phthalocyanine have good stability.
The eosin Y/zinc phthalocyanine composite PVA film has both saturated absorption and reverse saturated absorption, the absorption characteristics of the eosin Y/zinc phthalocyanine composite PVA film are not eliminated, and the composite material can overcome the defect of insufficient absorption of a single material. The saturation absorption of eosin Y is dominant at low light intensity, the anti-saturation absorption of zinc phthalocyanine is dominant at high light intensity, and the absorption characteristics of the two are complementary.
Further, the total absorption coefficient can be regulated and controlled by adjusting the proportion of the mass fraction, so that the mutual regulation between the saturated absorption and the anti-saturated absorption is realized, the nonlinear absorption coefficient beta is regulated, the addition of the limiting characteristic of the material is realized, and the aim of effectively regulating and controlling the output light intensity is fulfilled. The composite material can be used for novel optical limiters, optical switches, mode lockers and the like, and provides thought for manufacturing optical devices with specific absorption coefficients.
The experiment also carries out the characteristic research of the composite film of other partial materials, although some composite materials can simultaneously show the saturated absorption and the anti-saturated absorption characteristics, the excitation condition is very harsh, the effect of the composite PVA film without eosin Y/zinc phthalocyanine is ideal, and meanwhile, the nonlinear absorption coefficient is not easy to control by free adjustment.
Those of ordinary skill in the art will recognize that the embodiments described herein are for the purpose of aiding the reader in understanding the principles of the present invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (4)
1. The solution for preparing the composite film is characterized in that 1.5-3.0 parts of eosin Y and 45-65 parts of zinc phthalocyanine are added into 5000 parts of polyvinyl alcohol and 100000 parts of deionized water according to parts by weight to obtain mixed solution;
stirring the mixed solution for 1 hour at a constant temperature of 45 ℃ by using a magnetic stirrer;
stirring the mixed solution for 20 minutes by adopting ultrasonic waves with the frequency of 20kHz and the power of 20kW, cooling for 10 minutes, stirring for 2 hours at the frequency, and controlling the particle size of zinc phthalocyanine to be in a nano level by adopting ultrasonic stirring treatment;
finally, the uniformly mixed eosin Y/zinc phthalocyanine compound polyvinyl alcohol solution is obtained.
2. The solution for preparing a composite film according to claim 1, wherein,
1.5 parts of eosin Y; 5000 parts of polyvinyl alcohol; 65 parts of zinc phthalocyanine; 100000 portions of deionized water.
3. A method of preparing a composite film, comprising:
s1, preparing a polyvinyl alcohol solution with the mass fraction of 5%, wherein 50g of polyvinyl alcohol and 1000g of deionized water are prepared;
s2, adding 0.015-0.03 and g of eosin Y and 0.45-0.65g of zinc phthalocyanine into the polyvinyl alcohol solution obtained in the step S1;
s3, stirring the mixed solution obtained in the step S2 for 1 hour by using a magnetic stirrer at the constant temperature of 45 ℃, stirring the mixed solution obtained in the step S2 by using ultrasonic waves with the frequency of 20kHz and the power of 20kW for 20 minutes, cooling for 10 minutes, stirring the mixed solution for 2 hours at the frequency to obtain uniformly mixed eosin Y/zinc phthalocyanine composite polyvinyl alcohol solution, and controlling the size of zinc phthalocyanine particles to be in a nano level by using ultrasonic waves for stirring treatment;
s4, taking 10mL of uniformly mixed eosin Y/zinc phthalocyanine compound polyvinyl alcohol solution, casting the solution onto a clean glass substrate with the thickness of 9cm multiplied by 12cm, and horizontally placing the glass substrate in a clean darkroom for 4-5 days to obtain the eosin Y/zinc phthalocyanine compound polyvinyl alcohol film.
4. Use of the eosin Y/zinc phthalocyanine composite polyvinyl alcohol film obtained by the method of producing a composite film according to claim 3 for producing optical switches, limiters and mode lockers.
Priority Applications (1)
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| CN103293822B (en) * | 2013-05-16 | 2015-10-28 | 中北大学 | The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material |
| CN103319827B (en) * | 2013-07-02 | 2015-09-09 | 中国科学技术大学 | The preparation method of the inorganic nano combined film of a kind of You Ji – |
| CN103554443B (en) * | 2013-10-28 | 2015-12-09 | 中国工程物理研究院化工材料研究所 | Poly-(phenylacetylene support)-Phthalocyanine Zinc polymkeric substance with optical limitation and its preparation method and application |
| CN111458791A (en) * | 2020-03-12 | 2020-07-28 | 深圳大学 | All-optical diode based on two-dimensional material and preparation method thereof |
| CN112083616A (en) * | 2020-09-21 | 2020-12-15 | 中国科学院长春光学精密机械与物理研究所 | Metal-free phthalocyanine-graphene nonlinear optical composite material and preparation method and application thereof |
| CN113314929B (en) * | 2021-05-13 | 2022-05-20 | 长春理工大学 | Saturable absorber with saturable absorption and reverse saturable absorption characteristics and application thereof |
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