CN106206953B - A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and application - Google Patents

A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and application Download PDF

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CN106206953B
CN106206953B CN201610605190.9A CN201610605190A CN106206953B CN 106206953 B CN106206953 B CN 106206953B CN 201610605190 A CN201610605190 A CN 201610605190A CN 106206953 B CN106206953 B CN 106206953B
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molybdenum oxide
alcohol
interlayer materials
synthetic method
soluble
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张坚
熊健
李强
徐聪
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Ji'nan Changyao Engineering Technology Co Ltd
Guilin University of Electronic Technology
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Ji'nan Changyao Engineering Technology Co Ltd
Guilin University of Electronic Technology
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Abstract

The invention discloses a kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and applications, the present invention is using metal molybdenum powder as raw material, using hydrogen peroxide as oxidant, uses organic acid for stabilizer and cosolvent, using alcohols as proton donor, the molybdenum oxide powder of synthesis is a kind of non crystalline structure.The organic solar batteries device using this alcohol-soluble molybdenum oxide as boundary layer is also disclosed in this method.The molybdenum oxide that the present invention synthesizes has good alcohol-soluble matter, and filming performance is good, can uniformly form a film in transparent electrode and organic active layer, and low-temperature treatment may be implemented and compatible flexible substrate.The molybdenum oxide modified anode boundary layer, can effectively realize the extraction in hole, greatly promote the photoelectric efficiency of device.Such stabilizing material overcomes the unstability of electrode interface and organic layer interface to a certain extent simultaneously, so as to improve the stability of organic solar batteries.

Description

A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and application
Technical field
The invention belongs to organic solar batteries fields, and in particular to a kind of alcohol-soluble molybdenum oxide interlayer materials synthesis side Method and application.
Background technique
Energy problem is the significant problem for influencing human survival and sustainable development.Traditional fossil energy is the current energy Supply subject, but it belongs to non-renewable resources, has gradually used up totally.Fossil-fueled has resulted in serious simultaneously Environmental problem, living environment and health to the mankind cause serious threat.Solar battery belongs to since energy storage is huge In cleaning renewable resource, the substitute of best fossil energy is accepted extensively by the mankind and is considered as.It is well known that the energy Most general use form is electric energy, and converting the solar into electric energy has key effect to the large-scale application of solar energy. Therefore, the research and development of solar battery becomes the emphasis of various countries' concern.Organic solar batteries have lightweight, it is low at This, preparation process it is simple, translucent and flexible substrate can be compatible with realize extensive, high-speed production, and by extensive concern.But Be, device due to the biggish interface of physical attribute difference and organic layer material, with poor stability (RSC Adv., 2013, 3, 6188–6225).Still further aspect is that device efficiency is lower.Organic solar batteries device is small in recent years The peak efficiency of area always hover in 10 % or so (J. 2014,136,15,529 15532 Am. Chem. Soc., Scientific Reports, 2014, 4(4):6813-6813), it does not obtain important efficiency and breaks through.Efficiency and stability It can commercialized two big obstacle as organic solar batteries.So the organic solar batteries gesture for constructing efficient stable exists It must go.
Modifying interface, which can be compatible with, promotes device efficiency and device stability dual function, it is considered to be building efficient stable The effective means of organic solar batteries.Commercialized poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) (PEDOT: It PSS is) that usual anode modification material, the material have simple preparation, solution processable and to organic material with one now Fixed pervasive performance, and flexible substrate can be compatible with and realize large-scale production.But the material has highly acid, moisture pick-up properties, It can corrode the electrode material being modified and cause device extremely unstable.Seek the decorative material that preparation process is simple, stable to come Substitution PEDOT:PSS material is of great significance to the commercialization of organic solar batteries.
Molybdenum oxide has been widely applied to due to its suitable energy level, low evaporating temperature, stable physico-chemical property It is the alternative of the PEDOT:PSS more approved in terms of the anode modification of machine solar battery.The most common preparation of the material Method is the method using vapor deposition or sputtering, and such methods involve the equipment and complicated program of the valuableness such as vacuum, it is difficult to compatible Many vanguard technologies (such as roll-to-roll, inkjet printing, blade coating etc.), cause preparation cost high, are not suitable for extensive quotient Industry metaplasia produces.It is also had made some progress for solwution method prepares molybdenum oxide decorative layer at this stage, group method can return For three classes: the first kind be commercialized molybdenum oxide powder body material is directly dissolved in water formed aqueous solution (Journal of Materials Chemistry, 2012, 22(7): 3249-3254；Solar Energy Materials and Solar Cells, 2013, 109(109): 178-184；Advanced Functional. Materials 2012, 22(12): 2594-2605)；Second class using the aquation of polymolybdote prepare Electrochromic Molybdenum Oxide Coatings (Solar Energy Materials & Solar Cells, 2010, 94(5): 842-845)；Third class method be collosol and gel method (Advanced Energy Materials, 2012, 2(5): 523-527).In addition, using predecessor Mo (CO)3(EtCN)3, MoO2 (acac)2Also occur in succession preparing the reports of Electrochromic Molybdenum Oxide Coatings (Journal of Materials Chemistry, 2012, 22(7): 3249-3254；Solar Energy Materials and Solar Cells, 2013, 109(109): 178- 184；Advanced Functional. Materials 2012, 22(12): 2594-2605).
Existing solwution method is made a general survey of to prepare molybdenum oxide method and material there are several distinct issues:
1) the first and second class method is required to water as solvent, and the general filming performance of aqueous solvent is poor.In first kind method directly Commercialized molybdenum oxide powder is dispersed in aqueous solution, this suspension itself has unstability, is unfavorable for long term storage.From Material angle say always organic active layer be for water it is sensitive, water energy leads to the reduction of active layer performance and causes device interfaces Decaying, so aqueous solvent prepares molybdenum oxide boundary layer and is unfavorable for preparing the device of high stability.In addition, organic active layer surface one As be it is hydrophobic, so such methods synthesis molybdenum oxide can not form a film on active layer and be applied to be inverted device in；
2) preparation of third class method needs > 250 DEG C of high-temperature process to ensure carrier transport that film has had Energy.High heat treatment temperature can not be compatible with flexible substrate, can not be applied to be inverted device in (organic active layer cannot bear height Temperature processing).In addition, the Precursor Powder solubility property of sol-gal process synthesis is poor, the utilization rate of material is lower；
3) Mo (CO) is used3(EtCN)3, MoO2(acac)2To prepare Electrochromic Molybdenum Oxide Coatings.Such material has the oxygen of height Sensibility.
Existing method synthesis molybdenum oxide boundary layer have the shortcomings that one it is common, be to have height to treatment temperature Sensibility.
Alcohol-soluble is the highly desirable performance having of interlayer materials, because alcohol has good filming performance and hypotoxicity, The bad group for influencing device performance and stability will not be introduced in preparation process simultaneously.The present invention dissolves to solve molybdenum oxide Spend alcohol-soluble energy that is low, realizing height, the heat-treatment temperature range of Expansion Interface layer, compatible flexible substrate, realization solwution method oxygen Change molybdenum and proposes a feasible scheme in the problems such as application being inverted in device.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method and answers With.This method prepares molybdenum oxide forerunner's dry gel powder using follow-on sol-gel method.Have from method and material Following advantage:
The advantages of method: reaction raw materials are cheap in equipment cost, and the method improve traditional molybdenum oxides to synthesize routine side Case is acidified precursor solution using organic acids such as acetic acid, in organic acid-COOH group can adhere in the glue chain of colloidal sol, it can also It is present in the surface of micelle, should not be lost during low temperature drying.This alcohol-soluble group ensure that the xerogel has Good alcohol-soluble energy.Secondly, this kind of organic acid provides certain reducing agent for such molybdenum oxide as proton donor, it can be very well Regulation molybdenum oxide in+6 valence states molybdenum ion and+5 valence states molybdenum ion ratio.In order to realize further tune in this method The ratio of the molybdenum ion of+6 valence states and the molybdenum ion of+5 valence states is controlled, further second is done using alcohols solvent and gives proton processing, Which ensures that the presence of the molybdenum ion of+5 valence state a certain amount of in film, while alcohols is to having wide in range temperature after proton processing Degree processing tolerance, it is ensured that the xerogel after dry has temperature-insensitive.
The advantages of material: such aqueous precursor gel has excellent alcohol-soluble energy and filming performance.The alcoholic solution of xerogel With good stability, it is convenient for long term storage.The semiconducting behavior of such material is not with processing temperature fluctuation, performance simultaneously Temperature-insensitive out.The material of this method preparation is a kind of amorphous states of matter, the in this way cause for the continuity of film and height Close property lays the foundation.
Realizing the technical solution of the object of the invention is:
A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method: the following steps are included:
1) hydrogen peroxide is added in molybdenum powder, dissolves molybdenum powder；
2) organic acid addition step 1) is obtained into yellow solution solution；
3) the obtained yellow solution of step 2 is evaporated under reduced pressure, obtains xerogel；
4) xerogel for obtaining step 3) dilutes, and xerogel alcoholic solution is made；
5) xerogel alcoholic solution to be prepared in step 4) is dry, obtain molybdenum oxide powder；
6) the molybdenum oxide powder that will be obtained in step 5), is added in alcoholic solution, obtains alcohol-soluble molybdenum oxide boundary layer material Material.
The addition of 3 g molybdenum powders is placed in the beaker of ice bath in step 1), is then slowly added to 30 mL hydrogen peroxide, to double After oxygen water is added completely into, it is vigorously stirred 1-180 minutes.
In step 2, it will become orange-yellow from dark green to solution obtained in step 1), then 30 mL are added thereto to have Machine acid, system temperature is maintained between 20 DEG C -100 DEG C, and the retention time is 0.5-48 hours；
The organic acid is formic acid, acetic acid, propionic acid or citric acid.
In step 3), 10-100 DEG C of vapo(u)rizing temperature, until obtain yellow xerogel, by this xerogel again in drying box or true In empty drying box 10-150 DEG C it is 1-48 hours dry.
In step 4), the xerogel that step 3) is obtained is dissolved among alcoholic solution with the ratio of 1-50 mg/mL, and is added It hot 20-100 DEG C, stirs 1-48 hours.
In step 5), the color of solution to be prepared in step 4) is become into navy blue, is placed on 20-100 DEG C dry 1-48 hours in dry case, blue oxide molybdenum powder is obtained；
In step 6), the molybdenum oxide powder that will be obtained in step 5) is dissolved in alcoholic solution according to the concentration of 10-30mg/mL In, by the annealing of molybdenum oxide boundary layer, obtain alcohol-soluble molybdenum oxide interlayer materials.
The alcoholic solution is methanol, ethyl alcohol, isopropanol.
The molybdenum oxide interfacial layer thickness is 3-40nm.
The annealing temperature of the molybdenum oxide boundary layer is room temperature to 250 DEG C
Anode of the alcohol-soluble molybdenum oxide interlayer materials as organic solar batteries device made from above-mentioned synthetic method Application of the boundary layer in organic solar batteries.
Organic solar batteries device can be divided into eurymeric and reciprocal form structure,
Eurymeric structure: being from bottom to up hearth electrode, molybdenum oxide layer, organic active layer, electron transfer layer, top electrode；
Reciprocal form structure: being from bottom to up hearth electrode, electron transfer layer, organic active layer, molybdenum oxide layer, top electrode；
This material is using metal molybdenum powder as raw material, using hydrogen peroxide as oxidant, uses organic acid for acidulant, is with alcohols Proton donor, the molybdenum oxide powder of synthesis are a kind of non crystalline structures
The advantages of this synthetic method: reaction raw materials are cheap with equipment cost, are suitble to large-scale production, the interface material of preparation Expect forerunner's colloidal sol have height alcohol-soluble energy, solve dissolubility in conventional preparation techniques, film forming, device manufacturability it is each Kind problem.The temperature treatment regimes for successfully having widened this kind of decorative layer may be implemented at non-annealing processing and 250 DEG C of high annealings Reason is conducive to device in this way and prepares in the natural environment and normal use；This molybdenum oxide xerogel has good alcohol-soluble Can, it is soluble in methanol, ethyl alcohol, in isopropanol, overcomes application of the classic water-soluble molybdenum oxide in transoid device in this way Problem and the device stability problem that may cause.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of prepared molybdenum oxide powder in embodiment 1；
Fig. 2 is the SEM figure of prepared molybdenum oxide interface layer film in embodiment 1；
Fig. 3 is ITO/MoOx/PTB7:PC prepared in embodiment 171The AFM of BM schemes；
Fig. 4 is ITO/PEDOT:PSS/PTB7:PC prepared in 1 comparative example of embodiment71The AFM of BM schemes；
Under Fig. 5 illumination, ITO/MoO prepared by embodiment 1x/PTB7:PC71The I-V curve and comparative example of BM/Al device ITO/PEDOT:PSS/PTB7:PC71The I-V curve of BM/Al device；
Fig. 6 is ITO/MoO prepared by embodiment 1x/PTB7:PC71The air stability detection curve of BM/Al device and ITO/PEDOT:PSS/PTB7:PC prepared by comparative example71The air stability detection curve of BM/Al device.
Specific embodiment
With reference to the accompanying drawings and examples, the content of present invention is further elaborated, but is not limitation of the invention.
A kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method, comprising the following steps:
1) hydrogen peroxide is added in molybdenum powder, dissolves molybdenum powder,
2) by organic acid addition step 1) obtain to solution,
3) the obtained yellow solution of step 2 is evaporated under reduced pressure,
4) xerogel for obtaining step 3) dilutes,
5) solution to be prepared in step 4) is dry, molybdenum oxide powder is obtained,
6) the molybdenum oxide powder that will be obtained in step 5), is added in alcoholic solution, obtains alcohol-soluble molybdenum oxide boundary layer material Material.
The addition of 3 g molybdenum powders is placed in the beaker of ice bath in step 1), is then slowly added to 30 mL hydrogen peroxide, to double After oxygen water is added completely into, it is vigorously stirred 1-180 minutes；
In step 2, it will become orange-yellow from dark green to solution obtained in step 1), then 30 mL are added thereto to have Machine acid, system temperature is maintained between 20 DEG C -100 DEG C, and the retention time is 0.5-48 hours；
The organic acid is formic acid, acetic acid, propionic acid or citric acid；
In step 3), 10-100 DEG C of vapo(u)rizing temperature, until obtain yellow xerogel, by this xerogel again in drying box or true In empty drying box 10-150 DEG C it is 1-48 hours dry；
In step 4), the xerogel that step 3) is obtained is dissolved among alcohol solution with the ratio of 1-50 mg/mL, and 20-100 DEG C of heating is stirred 1-48 hours；
In step 5), the color of solution to be prepared in step 4) is become into navy blue, is placed on 20-100 DEG C dry 1-48 hours in dry case, blue oxide molybdenum powder is obtained；
Described, this molybdenum oxide powder may be dissolved in alcohols solvent.
In step 6), the molybdenum oxide powder that will be obtained in step 5 is dissolved in alcoholic solution according to the concentration of 10-30mg/mL In, by the annealing of molybdenum oxide boundary layer, alcohol-soluble molybdenum oxide interlayer materials are obtained,
The alcoholic solution is methanol, ethyl alcohol, isopropanol；
The molybdenum oxide interfacial layer thickness is 3-40nm；
The annealing temperature of the molybdenum oxide boundary layer is room temperature to 250 DEG C.
Anode of the alcohol-soluble molybdenum oxide interlayer materials as organic solar batteries device made from above-mentioned synthetic method Application of the boundary layer in organic solar batteries.
Organic solar batteries device can be divided into eurymeric and reciprocal form structure,
Eurymeric structure: being from bottom to up hearth electrode, molybdenum oxide layer, organic active layer, electron transfer layer, top electrode；
Reciprocal form structure: being from bottom to up hearth electrode, electron transfer layer, organic active layer, molybdenum oxide layer, top electrode；
Embodiment 1
The specific example of MoOx synthesis and raising OPV device efficiency and stability of the invention, device architecture are as shown in Figure 3 Eurymeric structure.Specific preparation step is divided into two parts explanation:
Molybdenum oxide boundary layer precursor solution preparation step is as follows:
1) hydrogen peroxide is added in molybdenum powder, dissolves molybdenum powder；
2) organic acid addition step 1) is obtained into yellow solution solution；
3) the obtained yellow solution of step 2 is evaporated under reduced pressure, obtains xerogel；
4) xerogel for obtaining step 3) dilutes, and xerogel alcoholic solution is made；
5) xerogel alcoholic solution to be prepared in step 4) is dry, obtain molybdenum oxide powder；
6) the molybdenum oxide powder that will be obtained in step 5), is added in alcoholic solution, obtains alcohol-soluble molybdenum oxide boundary layer material Material.
The addition of 3 g molybdenum powders is placed in the beaker of ice bath in step 1), is then slowly added to 30 mL hydrogen peroxide, to double After oxygen water is added completely into, it is vigorously stirred 60 minutes；
In step 2, it will become orange-yellow from dark green to solution obtained in step 1), then 30 mL vinegar are added thereto System temperature is maintained between 60 DEG C by acid, and the retention time is 12 hours；
In step 3), 50 DEG C of vapo(u)rizing temperature, until obtaining yellow xerogel, this xerogel is done in drying box or vacuum again 60 DEG C drying 48 hours in dry case；
In step 4), the xerogel that step 3) is obtained is dissolved among ethanol solution with the ratio of 10 mg/mL, and is added 50 DEG C of heat stirs 24 hours；
In step 5), the color of solution to be prepared in step 4) is become into navy blue, is placed on 60 DEG C of drying box In 12 hours, obtain blue oxide molybdenum powder；
In step 6), the molybdenum oxide powder that will be obtained in step 5 is dissolved in ethanol solution according to the concentration of 10-30mg/mL In, molybdenum oxide boundary layer is obtained into alcohol-soluble molybdenum oxide interlayer materials to annealing at 150 DEG C in room temperature,
The molybdenum oxide interfacial layer thickness is 10nm；
It is as follows using the organic solar batteries device preparation flow of molybdenum oxide boundary layer:
1) by commercially available ITO successively in acetone, dish washing liquid, deionized water is cleaned by ultrasonic in isopropanol, uses after cleaning It is dried with nitrogen, it is spare to be put into culture dish after ozone treatment 20min；
2) by MoOxIt is formed a film on ITO using spin coating process, film thickness about 10nm, 150 DEG C of annealings in thermal station, (N is transferred in glove box2Under atmosphere)；
3) the DIO mixed solution of the PTB7:PC71BM(1:1.5 of 25mg/mL) and 3% is spun on the speed of 1Krpm In MoOx film layer；
4) by the PTB7:PC71BM(1:1.5 of 25mg/mL) mixed solution, wherein the DIO of addition 3% changes for film morphology Property agent, is finally spun in PEDOT:PSS film layer with the speed of 1Krpm；
5) methyl alcohol process film surface is used later using 1 hour is vacuum-treated after spin coating；
6) device prepared is moved into vacuum evaporation instrument, vacuum is evacuated to 1 × 10-4 ~ 8 × 10-4 Pa hereinafter, adopting With the mask plate of strip with good conductive metals such as the bar shaped Al or Ag of speed vapor deposition 100nm thickness of 0.1-0.6nm/S.Cell area For 0.06cm2。
The parameters such as molybdenum oxide interface structure manufactured in the present embodiment, performance are embodied in attached drawing 1-6 respectively, below It is described with reference to the accompanying drawings:
The molybdenum oxide powder synthesized as can be seen from Figure 1 belongs to a kind of non crystalline structure.
Synthesized molybdenum oxide has good filming performance, obtained interface layer film densification nothing as can be seen from Figure 2 Hole；
It can be seen that on molybdenum oxide modification film from Fig. 3, with Fig. 4, PTB7:PC71The film morphology and PEDOT:PSS of BM PTB7:PC is formed by boundary layer71BM pattern is essentially identical；Roughness root mean square is respectively 1.39nm and 1.36nm
It is in 100mW/cm from Fig. 52The lower I-V curve of xenon lamp irradiation, digital sourcemeter is KEITHLEY 2400.It is bent Line 1 is ITO/MoOx/PTB7:PC71The I-V curve of BM/Al device；Curve 2 is Comparative Examples I TO/PEDOT:PSS/PTB7: PC71The I-V curve of BM/Al device.
It is as shown in table 1 to synthesize molybdenum oxide specific performance parameter.From Fig. 5 and table 1 as can be seen that based on molybdenum oxide boundary layer Device has certain advantage in performance parameter, and electric current is improved.From 14.57mA/cm2It is promoted to 15.19 mA/cm2。
1 comparative device of table and MoOxBoundary layer battery performance parameter
Sample Open-circuit voltage (V) Short circuit current (mA/cm2) Photoelectric conversion efficiency (%) Fill factor (%)
Molybdenum oxide interface layer device 0.72 15.19 7.47 68
Comparative device 0.73 14.57 7.31 68
Fig. 6 is PEDOT:PSS device prepared by molybdenum oxide interface layer device prepared by embodiment 1 and comparative example in sky Carried out the test curve figure of life test in 8 hours in gas, curve 1 be attenuation curve that MoOx is anodic interface layer device i.e. The efficiency attenuation curve of interface layer device prepared by embodiment 1, curve 2 are the effect that PEDOT:PSS is anodic interface layer device The efficiency attenuation curve of molybdenum oxide interface layer device prepared by rate attenuation curve, that is, comparative example 1, correlation curve 1,2 can be seen Out, use the device of MoOx by placing in air after 8 hours in example 1, originally photoelectric conversion efficiency stills remain in 80% or more of efficiency, and only 1 hour, efficiency have dropped more than 80% to comparative example device efficiency in air, by 8 After hour, device substantially completely fails.
Embodiment 2
Molybdenum oxide boundary layer precursor solution preparation step is as follows:
1) hydrogen peroxide is added in molybdenum powder, dissolves molybdenum powder,
2) by organic acid addition step 1) obtain to solution,
3) the obtained yellow solution of step 2 is evaporated under reduced pressure,
4) xerogel for obtaining step 3) dilutes,
5) solution to be prepared in step 4) is dry, molybdenum oxide powder is obtained,
6) the molybdenum oxide powder that will be obtained in step 5), is added in alcoholic solution, obtains alcohol-soluble oxidation _ molybdenum boundary layer Material.
The addition of 3 g molybdenum powders is placed in the beaker of ice bath in step 1), is then slowly added to 30 mL hydrogen peroxide, to double After oxygen water is added completely into, it is vigorously stirred 60 minutes；
In step 2, it will become orange-yellow from dark green to solution obtained in step 1), then 30 mL vinegar are added thereto System temperature is maintained between 60 DEG C by acid, and the retention time is 12 hours；
In step 3), 50 DEG C of vapo(u)rizing temperature, until obtaining yellow xerogel, this xerogel is done in drying box or vacuum again 60 DEG C drying 48 hours in dry case；
In step 4), the xerogel that step 3) is obtained is dissolved among ethanol solution with the ratio of 10 mg/mL, and is added 50 DEG C of heat stirs 24 hours；
In step 5), the color of solution to be prepared in step 4) is become into navy blue, is placed on 60 DEG C of drying box In 12 hours, obtain blue oxide molybdenum powder；
In step 6), the molybdenum oxide powder that will be obtained in step 5 is dissolved in ethanol solution according to the concentration of 10-30mg/mL In, the annealing temperature of molybdenum oxide boundary layer is room temperature, 60 DEG C, 150 DEG C, alcohol-soluble molybdenum oxide interlayer materials are obtained,
The molybdenum oxide interfacial layer thickness is 10nm；
It is as follows using the organic solar batteries device preparation flow of molybdenum oxide boundary layer:
1) by commercially available ITO successively in acetone, dish washing liquid, deionized water is cleaned by ultrasonic in isopropanol, uses after cleaning It is dried with nitrogen, it is spare to be put into culture dish after ozone treatment 20min；
2) MoOx is formed a film on ITO using spin coating process, film thickness about 10nm, this film using room temperature, 60 DEG C, 100 DEG C of processing；
3) the DIO mixed solution of the PTB7:PC71BM(1:1.5 of 25mg/mL) and 3% is spun on the speed of 1Krpm In MoOx film layer；
4) by the PTB7:PC71BM(1:1.5 of 25mg/mL) mixed solution, wherein the DIO of addition 3% changes for film morphology Property agent, is finally spun in PEDOT:PSS film layer with the speed of 1Krpm；
5) methyl alcohol process film surface is used later using 1 hour is vacuum-treated after spin coating；
6) device prepared is moved into vacuum evaporation instrument, vacuum is evacuated to 1 × 10-4 ~ 8 × 10-4 Pa hereinafter, adopting With the mask plate of strip with good conductive metals such as the bar shaped Al or Ag of speed vapor deposition 100nm thickness of 0.1-0.6nm/S.Cell area For 0.06cm2。
The device performance that it is obtained is as shown in table 2, and as can be seen from the table, such molybdenum oxide has very wide heat treatment temperature Spend range.
The device parameter performance that the molybdenum oxide boundary layer of 2 treatment of different temperature of table is presented
Molybdenum oxide boundary layer treatment temperature Open-circuit voltage (V) Short circuit current (mA/cm2) Photoelectric conversion efficiency (%) Fill factor (%)
Room temperature 17.42 0.71 50.76 6.32
60℃ 14.71 0.73 64.19 6.87
100℃ 14.83 0.72 66.32 7.10
Embodiment 3
Device architecture uses reciprocal form structure, and specific steps are divided into two parts and describe.
Molybdenum oxide boundary layer precursor solution preparation step is as follows:
1) hydrogen peroxide is added in molybdenum powder, dissolves molybdenum powder,
2) by organic acid addition step 1) obtain to solution,
3) the obtained yellow solution of step 2 is evaporated under reduced pressure,
4) xerogel for obtaining step 3) dilutes,
5) solution to be prepared in step 4) is dry, molybdenum oxide powder is obtained,
6) the molybdenum oxide powder that will be obtained in step 5), is added in alcoholic solution, obtains alcohol-soluble oxidation _ molybdenum boundary layer Material.
The addition of 3 g molybdenum powders is placed in the beaker of ice bath in step 1), is then slowly added to 30 mL hydrogen peroxide, to double After oxygen water is added completely into, it is vigorously stirred 60 minutes；
In step 2, it will become orange-yellow from dark green to solution obtained in step 1), then 30 mL lemons are added thereto Lemon acid, system temperature is maintained between 80 DEG C, and the retention time is 12 hours；
In step 3), 40 DEG C of vapo(u)rizing temperature, until obtaining yellow xerogel, this xerogel is done in drying box or vacuum again 80 DEG C drying 48 hours in dry case；
In step 4), the xerogel that step 3) is obtained is dissolved among ethanol solution with the ratio of 20 mg/mL, and is added 70 DEG C of heat stirs 24 hours；
In step 5), the color of solution to be prepared in step 4) is become into navy blue, is placed on 70 DEG C of drying box In 12 hours, obtain blue oxide molybdenum powder；
In step 6), the molybdenum oxide powder that will be obtained in step 5 is dissolved in methanol solution according to the concentration of 30mg/mL, The annealing temperature of molybdenum oxide boundary layer is room temperature, obtains alcohol-soluble molybdenum oxide interlayer materials,
The molybdenum oxide interfacial layer thickness is 8nm；
It is as follows using the organic solar batteries device preparation flow of molybdenum oxide boundary layer:
1) by commercially available ITO successively in acetone, dish washing liquid, deionized water is cleaned by ultrasonic in isopropanol, uses after cleaning It is dried with nitrogen, it is spare to be put into culture dish after ozone treatment 20min；
2) ZnO colloidal sol is formed a film on ITO using spin coating process, film thickness about 40nm, in thermal station at 250 DEG C of annealing Reason, is transferred in glove box (N2Under atmosphere)；
3) by the PTB7:PC71BM(1:1.5 of 25mg/mL) mixed solution, wherein the DIO of addition 3% changes for film morphology Property agent, is finally spun in PEDOT:PSS film layer with the speed of 1Krpm；
4) using 1 hour is vacuum-treated after spin coating, later using 60 DEG C 30 points of methyl alcohol process film surface and heating Clock；
5) prepared MoOx is formed a film on active layer using spin coating process, film thickness about 10nm；
6) device prepared is moved into vacuum evaporation instrument, vacuum is evacuated to 1 × 10-4 ~ 8 × 10-4 Pa hereinafter, adopting With the mask plate of strip with the good conductive metals such as the bar shaped Al or Ag of speed vapor deposition 100nm thickness of 0.1-0.6nm/S, cell area For 0.06cm2。

Claims (10)

1. a kind of alcohol-soluble molybdenum oxide interlayer materials synthetic method, which comprises the following steps:
1) hydrogen peroxide is added in molybdenum powder, dissolves molybdenum powder；
2) organic acid addition step 1) is obtained into yellow solution；
3) the obtained yellow solution of step 2) is evaporated under reduced pressure, obtains xerogel；
4) xerogel for obtaining step 3) dilutes, and xerogel alcoholic solution is made；
5) xerogel alcoholic solution to be prepared in step 4) is dry, obtain molybdenum oxide powder；
6) the molybdenum oxide powder that will be obtained in step 5), is added in alcoholic solution, obtains alcohol-soluble molybdenum oxide interlayer materials.
2. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 1, which is characterized in that will in step 1) The addition of 3g molybdenum powder is placed in the beaker of ice bath, is then slowly added to 30mL hydrogen peroxide, after being added completely into hydrogen peroxide, acutely Stirring 1-180 minutes.
3. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 1, which is characterized in that in step 2), Become orange-yellow completely to the solution in step 1), then thereto be added 30mL organic acid, by system temperature be maintained at 20 DEG C- Between 100 DEG C, the retention time is 0.5-48 hours；
The organic acid is formic acid, acetic acid, propionic acid or citric acid.
4. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 1, which is characterized in that in step 3), 10-100 DEG C of vapo(u)rizing temperature, until obtain yellow xerogel, the 10-150 DEG C of dry 1- in a vacuum drying oven again by this xerogel 48 hours.
5. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 1, which is characterized in that in step 4), The xerogel that step 3) is obtained is dissolved among alcohol solution with the ratio of 1-50mg/mL, and heats 20-100 DEG C, stirring 1-48 hours.
6. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 1, which is characterized in that in step 5), Solution colour to prepare in step 4) becomes navy blue, is placed in 20-100 DEG C of drying box 1-48 hours, obtains Blue oxide molybdenum powder.
7. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 1, which is characterized in that in step 6), The molybdenum oxide powder that will be obtained in step 5), is dissolved in alcoholic solution, by molybdenum oxide boundary layer according to the concentration of 10-30mg/mL It is made annealing treatment, obtains alcohol-soluble molybdenum oxide interlayer materials.
8. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 7, which is characterized in that the alcohol is molten Liquid be methanol, ethyl alcohol, isopropanol or in which two kinds.
9. alcohol-soluble molybdenum oxide interlayer materials synthetic method according to claim 7, which is characterized in that the oxidation Molybdenum interfacial layer thickness is 3-40nm, and annealing temperature is room temperature -- 250 DEG C.
10. alcohol-soluble molybdenum oxide interlayer materials made from the described in any item synthetic methods of claim 1-9 as it is organic too Application of the anode interface layer of positive energy battery device in organic solar batteries.
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