CN108359267A - A kind of photochemistry removes oxygen to protect the method and its application of the triplet excited state of photosensitizer - Google Patents
A kind of photochemistry removes oxygen to protect the method and its application of the triplet excited state of photosensitizer Download PDFInfo
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- CN108359267A CN108359267A CN201810245907.2A CN201810245907A CN108359267A CN 108359267 A CN108359267 A CN 108359267A CN 201810245907 A CN201810245907 A CN 201810245907A CN 108359267 A CN108359267 A CN 108359267A
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- photosensitizer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
Abstract
The present invention provides a kind of photochemistry and removes oxygen to protect the method and its application of the triplet excited state of photosensitizer, the method to be:Photosensitizer is added into solvent, and the solvent containing photosensitizer is irradiated using exciting light.Solvent is not necessarily to through the deoxygenations measure such as bubbling inert gas in the method for the invention, can solvent that directly illumination contains photosensitizer under air conditions can remove the oxygen in solvent, phosphorescence gradually becomes strong in a solvent.The invention further relates to using the method for the invention by gel carry out photoetching, and under air conditions realize triplet triplet annihilation photon on convert.
Description
Technical field
The invention belongs to nonlinear optical material field, it is related to a kind of photochemistry and removes oxygen to protect the triple of photosensitizer
The method and its application of excitation state.
Background technology
Triplet:Photosensitizer molecule in ground state, absorbs the exciting light of specific wavelength, and molecule jumps from ground state absorption energy
Singlet excited is adjourned, later due to the rigidity of molecule itself or molecule and heavy metal coordination, due to depositing for heavy metal effect
Under, intersystem crossing can occur for intermolecular energy, from singlet excited to triplet excited state.If molecule is directly from substance
Emitted energy returns to ground state to excitation state in the form of light, this process is fluorescent emission, and the service life is usually that nanosecond is other, if
Molecule transits to triplet from singlet excited, and from triplet, emitted energy returns to ground state in the form of light, this process is phosphorus
Light emitting.It is to violate spin rule due to transitting to triplet excited state from singlet excited, when this process needs certain
Between, thus the service life of phosphorescence for the service life of fluorescence, can big several orders of magnitude, generally microsecond rank.
Since the service life of phosphorescence can reach microsecond rank, the molecule oxygen in air is on energy level and symmetry and phosphorescence phase
Matching, therefore phosphorescence is easy to be quenched by the oxygen in air, makes the energy transfer of phosphorescent molecules triplet to oxygen, molecule
After oxygen receives the energy excitation of phosphorescence, from triplet transition to singlet state.Creating singlet oxygen is due to energy ratio molecule oxygen
Height, thus it is more unstable, it is easier to and oxidation occurs for organic compound, destroys organic matter.And the energy of phosphorescence is not logical
The form transmitting of light is crossed, but is quenched by oxygen, therefore phosphorescence is not easy to be detected under aerobic conditions.Phosphorescence biology at
Picture, OLED and organic compound identification etc. have boundless application, therefore phosphorescence is protected not quenched very by oxygen
It is significant.
Colloidal particle or macromolecule in colloidal sol or solution interconnect under certain condition, form space net structure,
It (can also be gas in xerogel, xerogel is also referred to as airsetting to be filled in structural void as the liquid of decentralized medium
Glue), such a special dispersion is referred to as gel.There is no mobility.It is internal often to contain big quantity of fluid.Inside gel
There is fine and close reticular structure, the transmission of solvent and molecule oxygen can be limited, therefore gel can be relatively good as one
Medium protects phosphorescence.Preparation process in terms of general gel is used to protect phosphorescence is under vacuum to be added to gelling agent
In solvent containing photosensitizer, by dissolving by heating gelling agent, after temperature cools down, gel is formed.
Conversion refers to that the donor in ground state is in laser or other light sources in spy on T-T annihilation photon
Under the irradiation of standing wave length, energy jump is absorbed to singlet excited, triplet excited state, Zhi Houyu are reached by intersystem crossing later
Acceptor molecule in ground state carries out energy transfer by collision, is given in triplet excited state in ground state by absorption is known from experience
The energy of body, from ground state transition to triplet excited state, the triplet excited state molecule of two receptors can collide with each other acceptor molecule
Realize energy transfer, it is possible to cause one of receptor to transit to singlet excited from triplet excited state, swash later from substance
Hair state sends out fluorescence and returns to ground state, another molecule for being in the receptor of triplet excited state is returned directly to after energy transmission is complete
Ground state.Here it sends out receptor and sends out the wavelength of fluorescence and be less than the wavelength of incident light.Due to the energy density of required exciting light
Low (usually less than 100mW/cm2), the advantages that absorbing ability is strong, upper conversion quantum yield is high, excitation-emission Wavelength tunable, TTA
Upper conversion is in field of solar energy utilization, three-dimensional mangement, fluorescent molecular biomarker and the high-tech areas such as photodynamics is for cancer
Show good application prospect and high additive value.
Invention content
For the technical problems in the prior art, a kind of photochemistry of present invention offer removes oxygen to protect photosensitizer
Triplet excited state method and its application, the method can simple effective method deprotect phosphorescence not by the oxygen in air
Gas quenches, and in terms of being applied and converting the two in photoetching and T-T annihilation photon.
In order to achieve the above objectives, the present invention uses following technical scheme:
Oxygen is removed it is an object of the present invention to provide a kind of photochemistry to protect the side of the triplet excited state of photosensitizer
Method, the method are:Photosensitizer is added into solvent, and the solvent containing photosensitizer is irradiated using exciting light.
As currently preferred technical solution, the solvent includes N-Methyl pyrrolidone, N- methyl morpholine oxides, 1,
In 3- Dimethyl Propylene Urea, 1,3- dimethyl-2-imidazolinones, dimethyl sulfoxide (DMSO) or tetramethylene sulfoxide any one or extremely
Few two kinds of combination, the combination is typical but non-limiting examples have:The group of N-Methyl pyrrolidone and N- methyl morpholine oxides
It closes, combination, 1,3- Dimethyl Propylene Urea and the 1,3- dimethyl -2- imidazoles of N- methyl morpholine oxides and 1,3- Dimethyl Propylene Urea
The combination of quinoline ketone, the combination of 1,3- dimethyl-2-imidazolinones and dimethyl sulfoxide (DMSO), dimethyl sulfoxide (DMSO) and tetramethylene sulfoxide
Combination or the combination of N-Methyl pyrrolidone, 1,3- dimethyl-2-imidazolinones and dimethyl sulfoxide (DMSO).
Wherein, the solvent that the present invention uses is not limited in above-mentioned cited solvent, can act on shape with singlet oxygen
All it can be used in the method for the invention at the solvent of peroxide.
As currently preferred technical solution, the photosensitizer includes Porphyrin-Based Sensitizer, phthalocyanines photosensitizer, metal
Complexing Polypyridine class photosensitizer, metal acetylene class photosensitizer, ring metal complex species photosensitizer and fluorine boron pyrylium dyes spread out
In biological species photosensitizer any one or at least two combination, the combination is typical but non-limiting examples have:Porphyrin
The combination of photosensitizer and phthalocyanines photosensitizer, the combination of phthalocyanines photosensitizer and metal complex Polypyridine class photosensitizer, metal
Combination, metal acetylene class photosensitizer and the ring metal complex species of Polypyridine class photosensitizer and metal acetylene class photosensitizer are complexed
The combination of photosensitizer, the combination of ring metal complex species photosensitizer and fluorine boron pyrylium dyes derivative species photosensitizer or porphyrin light
Quick dose, the combination etc. of phthalocyanines photosensitizer and metal complex Polypyridine class photosensitizer.
Preferably, the Porphyrin-Based Sensitizer includes porphyrin, the porphyrin containing substituent group or the metalloporphyrin complexing of amplification
In object any one or at least two combination, the combination is typical but non-limiting examples have:The porphyrin of amplification and contain
The combination of the porphyrin of substituent group, the combination of the porphyrin containing substituent group and metal porphyrin complex, metal porphyrin complex and expansion
The combination etc. of the porphyrin of combination or the amplification of the porphyrin of increasing, porphyrin and metal porphyrin complex containing substituent group.
Preferably, the phthalocyanines photosensitizer includes phthalocyanine, the phthalocyanine containing substituent group or the metal phthalocyanine complexing of amplification
In object any one or at least two combination, the combination is typical but non-limiting examples have:The phthalocyanine of amplification and contain
The combination of the phthalocyanine of substituent group, the combination of the phthalocyanine containing substituent group and metal phthalocyanine complex, metal phthalocyanine complex and expansion
The combination etc. of the phthalocyanine of combination or the amplification of the phthalocyanine of increasing, phthalocyanine and metal phthalocyanine complex containing substituent group.
Preferably, the metal include Li, Mg, Al, Ti, V, VO, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Pd, Ag, Re,
Os, Ir, Pt, Pb, U or UO2In any one or at least two combination, the combination is typical but non-limiting examples have:
The combination of Li and Mg, the combination of Mg and Al, Al and the combination of Ti, the combination of Ti and V, the combination of V and VO, the combination of Mn and Fe,
The combination of Co and Ni, the combination of Cu and Zn, Ga and the combination of Ru, the combination of Pd and Ag, the combination of Re and Os, Ir and Pt group
It closes, combination, U and the UO of Pb and U2Combination or Mg, Al and Ti combination etc..
The photosensitizer that the present invention uses can be Formulas I~IV compounds represented:
In the present invention, above-mentioned photosensitizer is added in above-mentioned solvent, solvent is irradiated by specific excitation wavelength, it is photosensitive
The energy of the triplet excited state of agent can be transferred to the molecular oxygen in solvent, and photosensitizer is excited by the energy of light, from ground state to
Up to singlet excited, triplet excited state is reached by intersystem crossing later, triplet excited state is quenched by molecule oxygen, generates list
Line state oxygen, singlet oxygen interact with solvent, gradually use up the oxygen in solvent.In the case where oxygen content gradually decreases,
Corresponding phosphorescence is gradually increased in this process, until reaching the maximum value under the light intensity.
As currently preferred technical solution, a concentration of the 5 × 10 of the photosensitizer-6~1 × 10-4Mol/L, such as 5 ×
10-6、8×10-6、1×10-5、2×10-5、5×10-5、8×10-5Or 1 × 10-4Deng, it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range.
As currently preferred technical solution, the optical energy density of the exciting light is 0.2mWcm-2~50mW cm-2,
Such as 0.2W cm-2、0.5W cm-2、1W cm-2、2W cm-2、5W cm-2、10Wcm-2、15W cm-2、20W cm-2、25W cm-2、
30W cm-2、35W cm-2、40W cm-2、45W cm-2Or 50W cm-2Deng it is not limited to cited numerical value, the numerical value
Other unrequited numerical value are equally applicable in range.
The excitation wavelength of the present invention is to refer to by photosensitizer from ground state transition to excitation state, in preferred implement, institute
The range for the excitation wavelength stated is from 300nm to 1600nm in range.
As currently preferred technical solution, the method is:To N-Methyl pyrrolidone, N- methyl morpholine oxides,
Any one in 1,3- Dimethyl Propylene Urea, 1,3- dimethyl-2-imidazolinones, dimethyl sulfoxide (DMSO) or tetramethylene sulfoxide is molten
Agent or at least two in the mixed solvent be added photosensitizer, photosensitizer concentration be 5 × 10-6~1 × 10-4Mol/L, and use light
Energy density is 0.2mW cm-2~50mW cm-2Exciting light irradiate the solvent containing photosensitizer, wherein the photosensitizer be porphin
Quinoline class photosensitizer, phthalocyanines photosensitizer, metal complex Polypyridine class photosensitizer, metal acetylene class photosensitizer, ring metal complex
In species photosensitizer and fluorine boron pyrylium dyes derivative species photosensitizer any one or at least two combination.
The second purpose of the present invention is to provide the application of the above method, the method is applied to photoetching and triplet-is triple
It is converted on state annihilation photon.
In the present invention, the method that the method for above-mentioned photochemistry deoxygenation is applied to field of lithography is:First, by gelator
It is added in the solution containing photosensitizer, according to the difference of the gelator of addition, passes through the side such as heating, heating-cooling or ultrasound
Method (when the gelator of addition can spontaneously form gel at room temperature, then without the method for above-mentioned promotion gel-forming), makes
Gelator is self-assembled into tridimensional network, forms gel.Since solvent contained in gel can carry out photochemistry deoxygenation,
And the tridimensional network that gelator is self-assembled into can limit the flowing of solvent and the diffusion of oxygen, therefore, in gel
It is consumed by the oxygen at illumination position, the photosensitizer at the position, which is excited after light irradiates, later can send out phosphorescence, show
The history of illumination.
According to the method for appeal photoetching, different pierced patterns can be placed on gel, light can only penetrate the portion of hollow out
Divide and be irradiated to gel, and then leaves the trace of illumination on gel.Therefore, light source can be used as one-pen, not touch gel
Under conditions of leave various patterns.
In the present invention, when the method for above-mentioned photochemistry deoxygenation is applied to convert on T-T annihilation photon, on
Solution system is converted by donor, receptor is formed with one of above-mentioned several solvents of deoxygenation are capable of;Donor should meet energy level with receptor
Matching, the triplet energy level of donor are higher than the triplet energy level of receptor;Two times of the triplet energy level of receptor are higher than singlet state energy
Grade, level-density parameter are conducive to upper conversion.The upper conversion told, can not be right under photosensitizer provided by the invention and receptor complex
Solution carries out conventional nitrogen and is bubbled deoxygenation, directly utilizes the laser excitation of some strength, is converted in realization.
In the present invention, the energy density for the exciting light converted on T-T annihilation photon is 5~1000mW cm-2, such as 5W cm-2、10W cm-2、15W cm-2、20W cm-2、100W cm-2、300Wcm-2、500W cm-2、800W cm-2、900W
cm-2Or 950W cm-2Deng it is not limited to cited numerical value, other unrequited numerical value are equally suitable in the numberical range
With.
In the upper conversion solution system that the present invention uses, the molar ratio of donor and receptor is 1:1~200, such as 1:1、1:2、
1:5、1:10、1:15、1:20、1:30、1:40、1:50、1:80、1:100、1:120、1:150、1:180 or 1:200 etc., but simultaneously
It is not limited only to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
In the present invention, the receptor used in being converted on T-T annihilation photon into organic dyestuff, be refer to and
Photosensitizer, which acts synergistically, reaches the corresponding organic molecule (receptor) of conversion, is shown in the range of 360nm to 750nm
The compound of fluorescent emission especially shows the fluorescent dye of fluorescent emission in the range of 360nm to 750nm.As DPA (9,
10- diphenylanthrancenes) can and PtOEP form red turn of indigo plant, BPEA can and PtTPBP be formed red turn it is green etc..The concentration one for the receptor told
As be 1 × 10-3mol·dm-3~2 × 10-3mol·dm-3, such as 1 × 10-3mol·dm-3、1.1×10-3mol·dm-3、1.2×
10-3mol·dm-3、1.3×10-3mol·dm-3、1.4×10-3mol·dm-3、1.5×10-3mol·dm-3、1。6×10- 3mol·dm-3、1.7×10-3mol·dm-3、1.8×10-3mol·dm-3、1.9×10-3mol·dm-3Or 2 × 10-3mol·
dm-3Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
In the present invention, the receptor used in being converted on above-mentioned T-T annihilation photon can be such as Formula V and Formula IV
Compound represented:
In the present invention, difference may be implemented by the selection of donor and acceptor compound and the allotment of concentration and ratio
The upper conversion of color, efficiency reach as high as 11%, can be applied to the fields such as photovoltaic and photocatalysis.
Compared with prior art, the present invention at least has the advantages that:
(1) present invention firstly discloses protect the side of the triplet excited state of photosensitizer by oxygen in illumination removing solvent
Method is interacted oxygen depleted with solvent and singlet oxygen so that solvent rouses inert gas deoxygenation without carrying out, without
It is operated in glove box, directly under air conditions, the process that phosphorescence gradually increases in a solvent can be observed by illumination;
(2) it present invention firstly discloses the special deoxygenation function using solvent, prepares gel and illumination shape is passed through to gel
At pattern, the pattern can there are a few hours on gel, and can quickly be wiped by destroying gel rubber system, pass through later
The modes such as gel selfreparing, heating-cooling or ultrasound gel again, repeats " wipe, write ";
(3) present invention be utilized for the first time be capable of illumination deoxygenation solvent apply on T-T annihilation photon turn
Field is changed, deoxygenation is carried out with illumination, avoids conversion component from being contacted with oxygen, solves the triplet of prior art photosensitizer
The problem of being quenched by oxygen, upper transfer efficiency is up to 11%, and in general upper transfer efficiency in the prior art is less than 10, take
Obtained unexpected technique effect;
(4) disclosed by the invention that conversion is carried out based on solvent deoxygenation protection triplet, it prepares simply, without complicated mistake
Journey, strong applicability can be obtained shining for a variety of upper conversion components, and safety and environmental protection, can be used in air, have practicality
Value is suitable for industrialized production;
(5) illumination deoxidation method provided by the invention can also be applied in photocatalysis, light therapy, solar cell and temperature
Degree sensor etc. is related to the field of triplet protection.
Description of the drawings
Fig. 1 is the mechanism schematic diagram that phosphorescence generates;
Fig. 2 is phosphorescence variation diagram of the photosensitizer in DMSO solution shown in Formulas I in embodiment 1;
Fig. 3 a are photoactivation phosphorescence spectrum of the photosensitizer in DMSO solution shown in Formulas I in embodiment 1;
Fig. 3 b are photoactivation phosphorescence spectrum of the photosensitizer in DMSO solution shown in formula III in embodiment 2;
Fig. 4 is the manufacturing process and photoetching process schematic diagram of gel;
Fig. 5 is to convert energy diagram on T-T annihilation photon;
Fig. 6 a are receptor shown in the donor shown in air conditions Formula Il in embodiment 5 and Formula V green turn in DMSO solution
Blue transition diagram;
Fig. 6 b are the donor shown in air conditions following formula I V and receptor red turn of green transition diagram in DMSO solution shown in Formula IV;
Fig. 7 a are receptor shown in the donor shown in air conditions Formula Il in embodiment 5 and Formula V green turn in DMSO solution
Blue light spectrogram;
Fig. 7 b, which are that receptor is red in DMSO solution shown in the donor shown in air conditions following formula I V and Formula IV, turns green light spectrogram.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1
A kind of photochemistry is provided in the present embodiment and removes oxygen come the method for protecting the triplet excited state of photosensitizer, the side
Method is:Photosensitizer shown in Formulas I is dissolved in DMSO, photosensitizer concentration is 1.0 × 10-4mol dm-3, use optical power density
For 70mW cm-2Ultraviolet light solution is irradiated, it is observed that phosphorescence is from scratch, gradually become strong process.Specific phosphorus
The change procedure of light is as shown in Fig. 2, spectrogram is as shown in Figure 3a.
Embodiment 2
A kind of photochemistry is provided in the present embodiment and removes oxygen come the method for protecting the triplet excited state of photosensitizer, the side
For method other than using photosensitizer shown in formula III, other conditions are same as Example 1.The variation spectrogram of phosphorescence such as Fig. 3 b institutes
Show
Embodiment 3
A kind of photochemistry is provided in the present embodiment and removes oxygen come the method for protecting the triplet excited state of photosensitizer, the side
Method is:Photosensitizer shown in Formulas I is dissolved in DMSO, photosensitizer concentration is 1.0 × 10-5mol dm-3, use optical power density
For 0.3mW cm-2Ultraviolet light solution is irradiated, it is observed that when optical power density is relatively low, the process of photoactivation
It takes relatively longer.
Embodiment 4
A kind of photochemistry is provided in the present embodiment and removes oxygen to protect the method for the triplet excited state of photosensitizer in photoetching
In application, the method for concrete application is:
By malonic acid and tetradecy lamine with mass ratio for 1:2 are dissolved in methanol solution, and ultrasonic reaction 20min is obtained after volatilizing methanol
To gelator.Photosensitizer shown in Formulas I is dissolved in DMSO solution, a concentration of 1.0 × 10-4mol dm-3, 20ml is contained
The DMSO solution of photosensitizer is poured into beaker, and gelator is put into the solution, and the mass ratio of gelling agent and solution is 4%
(w/w), the solid-liquid system is heated, heating temperature is 70 DEG C, until gelling agent is completely dissolved, is cooled to room temperature, waits for gel stability
Afterwards, it is inverted, pierced pattern is affixed on beaker bottom, the pierced pattern on beaker wall is attached to about using ultraviolet light (365nm) irradiation
2min, light source between pierced pattern at a distance from be 2cm, optical power density 75mWcm-2.The pattern being photo-etched into can keep several
Hour, but by heating quickly erasing photoetching can be re-started after cooling.Lithographic results are as shown in Figure 4.
Embodiment 5
A kind of photochemistry is provided in the present embodiment and removes oxygen to protect the method for the triplet excited state of photosensitizer triple
Application in being converted on state-triplet annihilation photon, the method for concrete application are:
Donor shown in Formula II is dissolved in receptor shown in Formula V in DMSO, and the molar ratio of donor and receptor is 1:200.Donor
A concentration of 1.0 × 10 in DMSO-5mol·dm-3, receptor is 2.0 × 10-3mol·dm-3, it realizes and converts in DMSO,
There are 2 kinds of patterns, respectively:
, directly to be carried out under air conditions, the DMSO solution containing donor and receptor of 5ml is positioned over container for the first
In, no any deoxygenation processing, it is directly to operate under air that donor and receptor, which are dissolved in DMSO,.It is irradiated using laser light source
The solution, as shown in Figure 6 a, the power of laser are greater than 10mWcm-2, 1s or so can be observed to be converted in apparent green turn of basket
The generation of phenomenon.Fig. 7 a are corresponding spectrogram.
Second is for the DMSO solution for containing donor and receptor is poured into container, fill and is sealed, uses ultraviolet source later
Irradiate solution 5min, after which carries out illumination deoxygenation, irradiate the solution with laser light source, occur at once green turn it is blue upper turn
Change phenomenon.
Embodiment 6-9
In the present embodiment, other than the solvent used is respectively TMSO, DMPU, DMI and NMP, other conditions with reality
It is identical to apply example 5.
Green turn is converted on the T-T annihilation photon carried out in embodiment 5-9, and blue the results are shown in Table 1.
Table 1
It can be seen that these types of solvent can be effectively removed oxygen protection triplet excited state from above table, and
Also it can be suitable for upper converting system, while achieve relatively good efficiency.It can be removed completely with nitrogen on oxygen scavenging ability
Oxygen mutually matches in excellence or beauty.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And the increase of accessory, the selection etc. of concrete mode, it all falls within protection scope of the present invention and the open scope.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (7)
1. a kind of method that photochemistry removes oxygen to protect the triplet excited state of photosensitizer, which is characterized in that the method is:
Photosensitizer is added into solvent, and the solvent containing photosensitizer is irradiated using exciting light.
2. according to the method described in claim 1, it is characterized in that, the solvent includes N-Methyl pyrrolidone, N- methyl oxygen
Change appointing in morpholine, 1,3- Dimethyl Propylene Urea, 1,3- dimethyl-2-imidazolinones, dimethyl sulfoxide (DMSO) or tetramethylene sulfoxide
It anticipates a kind of or at least two combinations.
3. method according to claim 1 or 2, which is characterized in that the photosensitizer includes Porphyrin-Based Sensitizer, phthalocyanines
Photosensitizer, metal complex Polypyridine class photosensitizer, metal acetylene class photosensitizer, ring metal complex species photosensitizer and fluorine boron
In pyrylium dyes derivative species photosensitizer any one or at least two combination;
Preferably, the Porphyrin-Based Sensitizer includes in the porphyrin of amplification, porphyrin or metal porphyrin complex containing substituent group
Any one or at least two combination;
Preferably, the phthalocyanines photosensitizer includes in the phthalocyanine of amplification, phthalocyanine or metal phthalocyanine complex containing substituent group
Any one or at least two combination;
Preferably, the metal include Li, Mg, Al, Ti, V, VO, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Pd, Ag, Re, Os,
Ir, Pt, Pb, U or UO2In any one or at least two combination.
4. according to claim 1-3 any one of them methods, which is characterized in that a concentration of the 5 × 10 of the photosensitizer-6~1
×10-4mol/L。
5. according to claim 1-4 any one of them methods, which is characterized in that the optical energy density of the exciting light is
0.2mW cm-2~50mW cm-2。
6. according to claim 1-5 any one of them methods, which is characterized in that the method is:To N-Methyl pyrrolidone,
N- methyl morpholine oxides, 1,3- Dimethyl Propylene Urea, 1,3- dimethyl-2-imidazolinones, dimethyl sulfoxide (DMSO) or tetramethylene are sub-
Photosensitizer is added in any one solvent in sulfone or at least two in the mixed solvent, and photosensitizer concentration is 5 × 10-6~1 × 10-4Mol/L, and the use of optical energy density is 0.2mW cm-2~50mW cm-2Exciting light irradiate the solvent containing photosensitizer,
Described in photosensitizer be Porphyrin-Based Sensitizer, phthalocyanines photosensitizer, metal complex Polypyridine class photosensitizer, metal acetylene class light
Any one in quick dose, ring metal complex species photosensitizer and fluorine boron pyrylium dyes derivative species photosensitizer or at least two
Combination.
7. a kind of application of any one of claim 1-6 the methods, which is characterized in that the method is applied to photoetching and triple
It is converted on state-triplet annihilation photon.
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CN112048076A (en) * | 2020-08-31 | 2020-12-08 | 广东工业大学 | Ternary supermolecule self-assembly up-conversion gel and preparation method and application thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN112048076A (en) * | 2020-08-31 | 2020-12-08 | 广东工业大学 | Ternary supermolecule self-assembly up-conversion gel and preparation method and application thereof |
CN114874610A (en) * | 2022-04-21 | 2022-08-09 | 苏州科技大学 | Red-blue double-peak gain light conversion material composition and preparation method and application thereof |
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