CN104945602B - The crosslinkable composition of conjugated polymer material, click chemistry containing alkenyl/alkynyl functionality - Google Patents
The crosslinkable composition of conjugated polymer material, click chemistry containing alkenyl/alkynyl functionality Download PDFInfo
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Abstract
The invention discloses the conjugated polymer material containing alkenyl/alkynyl functionality, the crosslinkable composition of click chemistry comprising the above-mentioned conjugated polymer material containing alkenyl/alkynyl functionality and the crosslinking agent with mercapto functional group.Composition of the invention is dissolvable in water in organic solvent, selectivity addition light trigger, insoluble insoluble polymer interpenetration network film is cross-linked to form under conditions of ultraviolet light or heating after solution processing film forming, reaction condition is simple, speed is fast, yield is high, environment-friendly；The miscible phenomenon in interface when solution processing can be overcome to prepare multilayer device between layers, is suitable to prepare complicated multilayer organic electronic device, applies in organic electro-optic device.
Description
Technical field
Organic semiconducting materials the present invention relates to be used for organic electro-optic device, more particularly to containing alkenyl/alkynyl functionality
Conjugated polymer material, the crosslinkable composition of click chemistry.
Background technology
Organic electro-optic device can prepare device due to organic semiconducting materials by solution processing mode, with light
Matter, it is flexible, can low cost prepare many merits of broad area device and attract wide attention.In order to prepare efficient device, have
Machine photoelectric device generally needs the device architecture of multilayer to improve the efficiency of device, but solution processing prepares multilayer device and needs solution
The miscible problem in interface between certainly organic interlevel layer and layer.And be one using cross-linking functional layer and overcome that what interface dissolved each other have
Effect method, but existing cross-linking method technological requirement is complicated at present, generally requires in high-temperature heating or long-time ultraviolet lighting, or
Both persons could realize crosslinking carry out simultaneously under conditions of, have a great impact to device performance (J.Mater.Chem.2008,
18,4495-4509)。
Sulfydryl-alkene/alkynes photochemical reaction as the important species in click chemistry, with having a wide range of application, reaction condition
Simply, many advantages, such as speed is fast, yield is high, environment-friendly, selectivity is strong, and alkene/alkynyl functionality is incorporated into conjugated polymers
On the side chain of thing, itself change very little to structure does not interfere with the intrinsic photoelectric property of material substantially, only serves participation and hands over
The effect of connection, therefore different purposes can be made it have by changing the structure of polymer conjugated main chain, have wide range of applications.
Existing sulfydryl-alkene/alkynes click chemistry composition is mostly degree of branching very high, the more non-co- molecular conjugate knot of number of functional groups
Structure, is prepared for polymer microballoon, and the field such as block polymer and highly-branched polymers, this class formation is not applied to substantially
In organic photoelectric field.
The content of the invention
In order to overcome the disadvantages mentioned above and deficiency of prior art, alkenyl/alkynyl is contained it is an object of the invention to provide one kind
The conjugated polymer material of functional group.
Another object of the present invention is to provide the point comprising the above-mentioned conjugated polymer material containing alkenyl/alkynyl functionality
Chemically-crosslinked composition is hit, there is good dissolubility in general organic solvent, and solution has certain chemistry steady
Qualitative, reaction condition is simple, speed is fast, yield is high, environment-friendly.
The purpose of the present invention is achieved through the following technical solutions：
Conjugated polymer material containing alkenyl/alkynyl functionality, with following structure：
Wherein, F is the crosslinked group containing alkenyl or alkynyl；A1 and A2 are the aromatic radical containing phenyl ring or thiophene derivant
Group；
R1 and R2 is straight chain, side chain or the ring-type alkyl group of C1~C22；Or be the alkyl with following structure：Alkyl
Upper one or more carbon atoms by the one kind in oxygen atom, aryl, hydroxyl, amido, carbonyl, carboxyl, ester group, cyano group, nitro or
Above functional group replaces, and hydrogen atom is by halogen atom oxygen atom, aryl, hydroxyl, amido, carbonyl, carboxyl, ester group, cyano group, nitro
In one or more functional groups substitution；
0<X≤1,0≤y<1, x+y=1；N is the degree of polymerization.
The A1 and A2 is fluorenes, carbazole, silicon fluorene, benzene thiophene, benzene, thiophene, bithiophene, thiophene pentalene, thiophene
Fen and thiophene are coughed up, one or more of Thienopyrroles diketone, pyrrolo-pyrrole-dione, indoles fluorenes, indole carbazole；Or tied for more than
One or more of derivative of structure.
The structure of the A1 and A2 is any one in following structure；Or for the derivative of following structure in it is any one
Kind：
The F is any one of following structure:
The crosslinkable composition of click chemistry, including above-mentioned conjugated polymer material containing alkenyl/alkynyl functionality and
Crosslinking agent with mercapto functional group；Have with two or more in the molecular structure of the crosslinking agent with mercapto functional group
The sulfydryl of reactivity；Alkenyl/alkynyl functionality and the mol ratio of mercapto functional group are 1 in composition:0.7~0.9.
The crosslinking agent with mercapto functional group is any one in following structure：
The crosslinkable composition of described click chemistry, also including light trigger, its consumption typically constitutes from composition quality
Between 0%~5%, specific consumption is because of the different differences of different initiator activities.
Shown light trigger is double (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl and 2- hydroxy-2-methyl -1- benzene
The mixture of base -1- acetone, or be dimethoxybenzoin.
The crosslinkable composition of described click chemistry, under illumination or heating condition, the click chemistry is crosslinkable
Composition crosslinks reaction, forms insoluble insoluble polymer interpenetration network film.
The crosslinkable composition of click chemistry of the invention, can occur free radical chain increasing under conditions of illumination or heating
Reaction long, its reaction mechanism is as follows：
Sulfydryl-alkene reaction：When ultraviolet light irradiation, initiator absorbs photon and cracks to form free radical, and free radical is near
The sulfydryl of mercaptan compound capture a hydrogen, mercaptan is converted to sulfydryl free radical, sulfydryl free radical attack electron rich double bond hair
Raw Radical Addition, and sulfydryl-alkene photochemical reaction is completed in the presence of thiol molecule, it is finally that typical polymerization is anti-
Answer termination procedure.
Sulfydryl-alkyne reaction：Mercaptan compound forms sulfydryl free radical, and the free radical occurs addition and formed with Alkyl alkynyl group
Unstable intermediate thioether-Vinyl radical, thioether-Vinyl radical captures one from neighbouring mercaptan compound
Hydrogen atom, forms sulfydryl alkene ether intermediate.Followed by a sulfydryl-alkene clicking chemistry process.Intermediate sulfydryl alkene ether enters
There is photochemical reaction in one step and sulfhydryl compound.
In practical application, linked is processed into film with conventional organic solvent first, under illumination or heating condition
Insoluble insoluble interpenetrating net polymer film is cross-linked to form, as carrier transport/implanted layer or the other functions layer of device
It is applied to the organic electronic device of sandwich construction.
The crosslinkable composition of click chemistry of the invention is applied to prepare organic photovoltaic cell device, specific steps are such as
Under：
High work function transparent electrode is formed on a transparent substrate；Cover hole transmission layer on the transparent electrodes again；In hole
Injected as hole/passed using the conjugated polymer material of sulfydryl-alkene/alkynes crosslinking in transport layer or directly on electrode
Defeated layer；Process to form light absorbing zone with conjugated polymer on hole transmission layer；Being formed on light absorbing zone reduces work function
Cathodic modification layer；Metal cathode electrode is finally formed in cathodic modification layer again.
The transparent substrates are glass, PET or lucite；The transparency electrode is indium oxide
Tin, fluorine-doped tin oxide, Graphene or CNT；The material of the hole transmission layer is molybdenum trioxide, tungstic acid, five oxygen
Change two vanadium, poly- (3,4- dioxyethylene thiophene), poly- (styrene sulfonic acid) or polyaniline；The material of the cathodic modification layer be water/
The polyelectrolyte material of alcohol-soluble, side-chain radical amino-contained, quaternary ammonium salt group, phosphate radical, phosphate-based, sulfonate radical, carboxyl and
One or more conjugated polymer in hydroxyl, lithium fluoride, cesium fluoride, cesium carbonate, zinc oxide, titanium oxide；；The metal sun
The material of pole electrode is one or more of gold, aluminium, copper, silver, indium, nickel, lead, barium, calcium, magnesium and tin.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) present invention provide sulfydryl-alkene/alkynes cross-linking reaction linked, including conjugated polymer material, containing mercapto
Based cross-linker and light trigger all have good dissolubility in general organic solvent, and the polymer solution for obtaining has one
Determine chemical stability.Blend solution turns into solid film by processing after solvent volatilization, by after illumination or heating, can be with
Insoluble insoluble interpenetrating net polymer film is formed, therefore when multilayer device is constructed, boundary between layers can be overcome
The miscible phenomenon in face, can apply in the middle of the multilayer organic electro-optic device of whole soln processed complex.
(2) sulfydryl-alkene/alkyne reaction as click chemistry one kind, with having a wide range of application, reaction condition is simple, speed
Hurry up, many advantages, such as yield is high, environment-friendly, selectivity is strong, therefore prepare simply rapid during material, efficiency high, low cost, only
Need illumination in short-term or low-temperature heat, the influence for molded other functions layer is little, can replace completely processing method compared with
Complicated zinc oxide or titanium oxide etc..
(3) present invention is incorporated on the side chain of conjugated polymer by by alkene/alkynyl functionality, and itself changes to structure
Become very little, the intrinsic photoelectric property of material is not interfered with substantially, only serve the effect for participating in crosslinking, therefore can be poly- by changing
The structure of compound conjugated main chain reaches different purposes, has wide range of applications.
(4) present invention provide polymer solution can by way of spin coating, printing, inkjet printing ITO electrode, commonly use
Hole transmission layer applies a thin layer when needing, and is then crosslinked it, and device preparation technology is simple；
(5) conjugated polymer material containing alkenyl/alkynyl functionality of the invention has good heat endurance and electrification
Learn stability；
(6) the conjugated polymer thin layer that sulfydryl-alkene of the invention/alkynes cross-linking reaction is formed can significantly improve device
Energy.
Brief description of the drawings
Fig. 1 is poly- { 2,6- [(the 2- ethyl hexyls of 4,4- bis- of the conjugated polymer material with alkenyl-functional groups of embodiment 1
Base)-Dithiophene [3,2-b:2', 3'-d] thiophene coughs up] -co- 1,3- [5- (7- octenyls)-thiophene [3,4-c] pyrroles -4,6- two
Ketone] } film after (referred to as PDTSTPDE) crosslinking, the abosrption spectrogram before being embathed through chlorobenzene and after embathing；
Fig. 2 is that the conjugated polymer material PDTSTPDE with alkenyl-functional groups prepared by embodiment 1 is crosslinked through sulfydryl-alkene
Afterwards as hole injection/transport layer, material of main part is respectively applied to for PCDTBT：PC71BM and PDTSTPD：PC71The sun of BM
The change of corresponding density of photocurrent-voltage curve in battery device；
Fig. 3 is that the conjugated polymer material PDTSTPDE with alkenyl-functional groups prepared by embodiment 1 is crosslinked through sulfydryl-alkene
Afterwards as hole injection/transport layer, material of main part is respectively applied to for PCDTBT：PC71BM and PDTSTPD：PC71The sun of BM
The change of external quantum efficiency spectrum corresponding in battery device；
Fig. 4 is that the conjugated polymer material PDTSTPDE with alkenyl-functional groups prepared by embodiment 1 is crosslinked through sulfydryl-alkene
Afterwards as hole injection/transport layer, material of main part is applied to for PCDTBT：PC71Corresponding sky in the solar cell device of BM
Cave electric current；
Fig. 5 is that the conjugated polymer material PDTSTPDE with alkenyl-functional groups prepared by embodiment 1 is crosslinked through sulfydryl-alkene
Afterwards as hole injection/transport layer, material of main part is applied to for PDTSTPD：PC71Corresponding sky in the solar cell device of BM
Cave electric current.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
Poly- { 2,6- [4,4- bis- (2- ethylhexyls)-Dithiophenes of conjugated polymer containing alkenyl-functional groups of the present embodiment
[3,2-b:2', 3'-d] thiophene coughs up] -co- 1,3- [5- (7- octenyls)-thiophene [3,4-c] pyrroles -4,6- diketone] } (referred to as
PDTSTPDE synthetic route) is as follows：
(1) monomer 1 [the bromo- 5- hydrogen of 1,3- bis--thiophene [3,4-c] pyrroles -4,6- diketone] is according to document
Prepared by method disclosed in [Adv.Mater., 2011,23,1660], [4,4- bis- (2- the ethylhexyls) (front threes of -2,6- bis- of monomer 3
Ji Xi)-Dithiophene [3,2-b:2', 3'-d] thiophene coughs up] it is open according to document [J.Am.Chem.Soc., 2008,130,16144]
Method prepare.
(2) preparation of monomer 2 [bromo- 5- (7- octenyls)-thiophene [3,4-c] pyrroles -4,6- of 1,3- bis- diketone].By monomer
Bromo- 5- hydrogen-thiophene [3,4-c] pyrroles -4,6- diketone (1.244g, the 4mmol) of 1,3- bis- is dissolved in 8mL N, N- dimethyl formyls
In amine, stirred at room temperature 1 hour after adding sodium hydride (0.124g, 5.2mmol), then this solution be added drop-wise to 50 DEG C of 8-
In the DMF solution of bromo- 1- octenes (2.29g, 12mmol), with the dichloro of 150mL after being stirred at room temperature 12 hours
Methane is extracted, and is washed with water three times, and organic layer solution is dried with anhydrous magnesium sulfate, filtering and concentrating, after purified with silica gel chromatographic column,
Eluent is the mixed solvent of petroleum ether and dichloromethane, finally obtains white, needle-shaped crystals product, yield with ethyl alcohol recrystallization
It is 66%.
The nuclear magnetic data of product is as follows：1H NMR(300MHz,CDCl3):δ (ppm)=5.78 (m, 1H), 4.96 (m, 2H),
3.59(t,2H),2.02(m,2H),1.63(m,2H),1.34(m,6H).13C NMR(75MHz,CDCl3):δ (ppm)=
160.37,138.91,134.80,114.31,112.94,38.78,33.63,28.65,28.58,28.18,26.62.MS
(APCI,m/z):calcd.for C14H15Br2NO2S[M+1]+:422.00；found,422.10.
(3) polymer poly { 2,6- [4,4- bis- (2- ethylhexyls)-Dithiophene [3,2-b:2', 3'-d] thiophene coughs up] -co- 1,
3- [5- (7- octenyls)-thiophene [3,4-c] pyrroles -4,6- diketone] } (referred to as PDTSTPDE) preparation：
By bromo- 5- (7- octenyls)-thiophene [3,4-c] pyrroles -4,6- of monomer 1,3- bis- diketone (106.5mg,
0.253mmol) with monomer 4,4- bis- (2- ethylhexyls) -2,6- two (tin trimethyl)-Dithiophene [3,2-b:2', 3'-d] thiophene coughs up
(197.4mg, 0.265mmol) is dissolved in the mixed solvent of 5mL toluene and 0.5mL DMFs, argon gas ventilation 15
Minute, add (23mg, 8%) four to be taken a breath again 5 minutes after closing triphenyl phosphorus palladium catalyst, 115 DEG C of reactions 42 under argon gas protection
Hour, reacted again 3.5 hours after adding 80 μ L 2- (tributyl tin) thiophene, reaction 4 is small after then adding 100 μ L 2- bromothiophenes
When, it is down to room temperature and stops reaction, precipitation is separated out during reaction solution is instilled into 300mL methyl alcohol, solid product is filtrated to get, dry and be used in combination
Apparatus,Soxhlet's uses n-hexane successively, and dichloromethane extracting is finally washed lower product, methyl alcohol is instilled after concentration chloroformic solution with chloroform
Middle precipitation product, filtering drying obtains atropurpureus solid product, and yield is 80%.
The nuclear magnetic data of gained solid is as follows：1H NMR(300MHz,CDCl3):δ (ppm)=8.45 (s, 1H), 7.39 (s,
1H),5.81(m,1H),4.97(m,2H),3.69(br,2H),2.4-0.2(m,44H).
PDTSTPDE manufactured in the present embodiment has following structure：
Embodiment 2
The present embodiment with conjugated polymer material PDTSTPDE, double (2,4, the 6- trimethylbenzenes of 1,8- pungent two mercaptan and phenyl
Formoxyl) phosphine oxide：2- hydroxy-2-methyl -1- phenyl -1- acetone (1:4, mass ratio) composition composition as a example by illustrate such
Composition has the performance of anti-solvent wash-out after treatment.
Conjugated polymer material PDTSTPDE in embodiment 1 is completely dissolved in chlorobenzene, concentration is 15 mg/mls,
Pungent two mercaptan of a certain amount of 1,8- is added, alkenyl-functional groups are 1 with the mol ratio of mercapto functional group:0.8；Chain is repeated with polymer
The mol ratio of section is about 0.4:1, volume ratio accounts for the 4% of polymer chlorobenzene solution.Then add and account for PDTSTPDE mass 3%
Light trigger (double (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl and 2- hydroxy-2-methyl -1- phenyl -1- acetone
Mixture, mass ratio is 1：4).The UV testers (HP 8453spectrophotometer) produced with Hewlett-Packard test thin
The absorbance of film, front and rear absorbance contrast is embathed as shown in fig. 1 after the crosslinking of PDTSTPDE film forming in chlorobenzene solvent.Film forming is crosslinked
It is with the process of embathing：Using spin coating instrument, the solution drop of general 50 μ l is attached in the quartz substrate of 2cm × 1cm, then rotation lining
Bottom forms uniform film, and thickness is 40 rans, and then film is irradiated 5 seconds under the ultraviolet light that wavelength is 365 nanometers
Clock, the crosslink polymer network film for ultimately forming insoluble in organic solvent for 10 minutes is heated in 50 DEG C in heating plate.Use chlorobenzene
Spin coating is repeatedly cleaned on solvent PDTSTPDE films after cross-linking.PDTSTPDE after UV testers measure crosslinking
Absorbance change of the film before and after by chlorobenzene cleaning, contrast is as shown in Figure 1, it can be seen that the crosslinking degree of film.Absorbance
Decline is more, shows that more how uncrosslinked polymer is washed off by chlorobenzene, i.e., the degree of cross linking is low；Absorbance decline is fewer, then explanation is got over
Heteropolymer is crosslinked not to be washed off successfully and by chlorobenzene, i.e., the degree of cross linking is high.Analyzed by Fig. 1, chlorobenzene is used again after crosslinking
After solvent cleaning, the absorbance of PDTSTPDE films does not almost decline, and original absorbance is kept close to 100%.This explanation
PDTSTPDE films are very high through ultraviolet irradiation and heating post-crosslinking efficiency, have excellent anti-solvent elution property after crosslinking.
Cushion determines with sol evenning machine (KW-4A) high speed spin coating, thickness by solution concentration and rotating speed, uses surface profiler
(Tritek companies Alpha-Tencor-500 types) actual measurement monitoring.
Embodiment 3
The sun for injecting/transmitting layer material as hole using cross-linking conjugated polymer thin films PDTSTPDE of the present embodiment
The specific preparation process of battery device is as follows：
3,4-ethylene dioxythiophene monomer：Poly styrene sulfonate (PEDOT：PSS) aqueous dispersions are purchased from Bayer companies.
The solar cell active layer material that device is used, poly- [[9- (1- octyl groups nonyl) -9H- carbazole -2,7- diyls] -2,5- thiophene
Diyl -2,1,3- diazosulfide -4,7- diyl -2,5- thiophene diyl] (PCDTBT) purchase is from 1-Material companies；It is poly-
{ 2,6- [4,4- bis- (2- ethylhexyls)-Dithiophene [3,2-b:2', 3'-d] thiophene coughs up] -co- 1,3- [5- octyl thiophenes [3,4-c]
Pyrroles -4,6- diketone] } (PDTSTPD), it is according to method disclosed in document [J.Am.Chem.Soc., 2008,130,16144]
Prepare；The derivative small molecule [6,6] of carbon 70-phenyl-C71 butyric acid methyl esters (PC71BM) buy from Sigma-Adlrich companies.
Some with lot number ITO substrates, specification is 15 millimeters × 15 millimeters, and square resistance is about 20 ohm/, successively with third
Ketone, micron level semiconductor special purpose detergent, deionized water, ultrasonically treated 10 minutes cleaning ITO substrate surfaces of isopropanol, then put
Enter to stand 4 hours at 80 DEG C in constant temperature oven and dry.ITO substrates after drying are banged with oxygen plasma etch instrument with plasma
The organic impurities for removing the attachment of ITO substrate surfaces for 10 minutes is hit, model Baytron P VP AI are then used on ITO
4083 PEDOT：The film of the aqueous dispersions spin coating about 40nm of PSS is used as hole transmission layer.After film forming, transfer the sample into and add
140 DEG C are heated 20 minutes in thermal station, and above step is completed in an atmosphere.Finally just will be with PEDOT：The ITO substrates of PSS layer
It is transferred into nitrogen glove box.
Composition in embodiment 2 is dissolved in chlorobenzene, the mass concentration of PDTSTPDE is 3.8 mg/mls, 1,8
The volume fraction of pungent two mercaptan is 1vol%, light trigger (double (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl and 2- hydroxyls
The mixture of base -2- methyl isophthalic acids-phenyl -1- acetone, mass ratio is 1：4) the 3% of polymer quality is accounted for.In PEDOT：Revolved on PSS
PDTSTPDE solution is applied, is then dried and is removed solvent, obtain the dry film that thickness is 6 rans.Ultraviolet light 5 seconds it
Afterwards, cross-linked network PDTSTPDE films are formed it within 10 minutes in heating in 50 DEG C of heating plate.
Will be dissolved with PDTSTPD：PC71The chlorobenzene solution of BM or dissolved with PCDTBT：PC71The o-dichlorohenzene of BM：Chlorobenzene mixes
The solution light-absorption layer of spin coating into solar cell on this hole transmission layer.Wherein PDTSTPD：PC71The mass ratio of BM is 1：2,
Concentration in chlorobenzene solution is 8 mg/mls, and chlorobenzene solution adds pungent two mercaptan of 1,8- of 3vol%, and the rotating speed of spin coating is
1000 revs/min, thickness measurement is 90 rans；PCDTBT：PC71The mass ratio of BM is 1：4, concentration in a solvent is 5
Mg/ml, solvent is by o-dichlorohenzene and chlorobenzene according to 1：3 volume ratio configuration, the rotating speed of spin coating is 800 revs/min, thickness
It is determined as 85 rans.Thickness is determined with Alpha-Tencor-500 surface profilers.Afterwards in active layer spin coating one
The PFN of 5 ran of layer, PFN are dissolved in methyl alcohol：Acetic acid=100：In the mixed solvent of 1 (volume ratio), concentration be 0.2 milligram/
Milliliter, the rotating speed of spin coating is 2000 revs/min.One layer of 100 metal of ran is deposited finally by the method for vacuum evaporation
Aluminium.The active parts area of device is determined by mask in the region of ITO interaction lids, is 0.16 square centimeter.All preparation process
Carried out in the glove box of offer nitrogen atmosphere except aluminium electrode evaporation is outer, and be deposited with aluminium electrode to be in vacuum is 1 × 10-6In the least
Carried out in the plating storehouse of bar.
Device performance test is carried out under the irradiation of the type AM 1.5G sun optical analog lamps of Oriel 91192, and irradiation level is
1000 watts/square metre, current -voltage curve is measured using the type digital sourcemeters of Keithley 2400, so as to obtain energy conversion
The key parameters such as efficiency.To show that sulfydryl of the present invention-alkene is crosslinked the effect of PDTSTPDE hole transmission layers, contrast knot
Fruit is as shown in table 1.
Table 1
Table 1 and Fig. 2 show, based on PCDTBT：PC71BM and PDTSTPD：PC71In the solar cell of BM systems, increase
Conjugated polymer material PDTSTPDE with alkenyl-functional groups after the hole transmission layer that sulfydryl-alkene is crosslinked, device
Performance parameter significantly improve.
Fig. 3 shows the sky that the conjugated polymer material PDTSTPDE with alkenyl-functional groups is crosslinked through sulfydryl-alkene
Cave transport layer increased the external quantum efficiency of device, in PCDTBT：PC71The significant work for increasing and absorbing is served in BM systems
With.
Fig. 4 and Fig. 5 show the curve of the hole current density-effective voltage of device, by be fitted obtain device etc.
Effect hole mobility.Based on PCDTBT：PC71The system of BM, when not having PDTSTPDE cross-linked layers, the hole mobility of device is
1.1×10-4cm2V-1s-1, after increasing PDTSTPDE cross-linked layers, hole mobility is 3.6 × 10-4cm2V-1s-1；And be based on
PDTSTPD：PC71BM systems, when not having PDTSTPDE cross-linked layers, the hole mobility of device is 8.7 × 10-4cm2V-1s-1, increase
Plus after PDTSTPDE cross-linked layers, hole mobility is 3.9 × 10-3cm2V-1s-1.It can be seen that PDTSTPDE cross-linked layers can effectively change
Enter the hole transport performance of organic photovoltaic cell.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (6)
1. the conjugated polymer material of alkenyl/alkynyl functionality is contained, it is characterised in that with following structure：
Wherein, F is the crosslinked group containing alkenyl or alkynyl, and its structure is any one of following structure：
A1 and A2 are any one of following structure：
R1 and R2 is straight chain, side chain or the ring-type alkyl group of C1~C22；Or be the alkyl with following structure：One on alkyl
Individual or multiple carbon atoms are by one or more in oxygen atom, aryl, hydroxyl, amido, carbonyl, carboxyl, ester group, cyano group, nitro
Functional group replaces, and hydrogen atom is by halogen atom, oxygen atom, aryl, hydroxyl, amido, carbonyl, carboxyl, ester group, cyano group, nitro
One or more functional groups substitution；
0<X≤1,0≤y<1, x+y=1；N is the degree of polymerization；
The described conjugated polymer material containing alkenyl/alkynyl functionality is used to prepare the hole transport in solar cell device
Layer.
2. the crosslinkable composition of click chemistry, it is characterised in that including described in claim 1 containing alkenyl/alkynyl functionality
Conjugated polymer material and the crosslinking agent with mercapto functional group；The molecular structure of the crosslinking agent with mercapto functional group
In there is the sulfydryl of reactivity with two or more；The mol ratio of alkenyl/alkynyl functionality and mercapto functional group in composition
It is 1:0.7~0.9.
3. the crosslinkable composition of click chemistry according to claim 2, it is characterised in that described with mercapto functional group
Crosslinking agent be any one in following structure：
4. the crosslinkable composition of click chemistry according to claim 2, it is characterised in that also including light trigger.
5. the crosslinkable composition of click chemistry according to claim 4, it is characterised in that shown light trigger is phenyl
The mixture of double (2,4,6- trimethylbenzoyl) phosphine oxides and 2- hydroxy-2-methyl -1- phenyl -1- acetone, or to rest in peace
Fragrant dimethyl ether.
6. the crosslinkable composition of click chemistry according to any one of claim 2~5, it is characterised in that in illumination or
Under heating condition, the crosslinkable composition of click chemistry crosslinks reaction, forms insoluble insoluble polymer IPN net
Network film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105694051B (en) * | 2016-02-05 | 2018-07-06 | 山东师范大学 | Metal organic frame cross linking membrane based on click chemistry and preparation method and application |
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| CN109161002A (en) * | 2018-06-30 | 2019-01-08 | 华南理工大学 | N-shaped conjugated polymer based on alcoxyl thiophene alkynes unit and its application in organic photovoltaic |
| CN111484513B (en) * | 2019-05-21 | 2022-09-09 | 广东聚华印刷显示技术有限公司 | Borane derivative, preparation method thereof and electroluminescent device |
| CN111019094B (en) * | 2019-12-06 | 2020-10-30 | 华中科技大学 | Isopoly-trienylene cross-conjugated polymer, and preparation and application thereof |
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