CN105591031B - A kind of binary channels parallel connection type organo-mineral complexing solar cell based on first crystalline state porous nano germanium film - Google Patents

A kind of binary channels parallel connection type organo-mineral complexing solar cell based on first crystalline state porous nano germanium film Download PDF

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CN105591031B
CN105591031B CN201610167336.6A CN201610167336A CN105591031B CN 105591031 B CN105591031 B CN 105591031B CN 201610167336 A CN201610167336 A CN 201610167336A CN 105591031 B CN105591031 B CN 105591031B
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organic
germanium film
porous nano
heterojunction
layer
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CN105591031A (en
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倪牮
孙小香
张建军
李昶
蔡宏琨
张德贤
李娟�
许芮
李正龙
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Nankai University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

A kind of binary channels parallel connection type organo-mineral complexing solar cell based on first crystalline state porous nano germanium film, based on the first crystalline state porous nano germanium film with n-type conductive features, in the organic donor of spin coating thereon/organic receptor active layer, organic donor/inorganic acceptors form planar heterojunction while organic donor/organic receptor forms bulk-heterojunction.In the composite construction that this bulk-heterojunction and planar heterojunction coexist, carrier can realize that the binary channels of parallel way transports, and then strengthen while improving battery and transporting performance and expand absorption of the battery to solar spectrum.Wherein, the first crystalline state porous nano germanium film of n-type conductive features is using capacity plate antenna coupling plasma enhancing chemical vapor deposition（PECVD）System is prepared at room temperature.The advantage of the invention is that：Carrier binary channels transfer ways in parallel are combined with the characteristic of germanium material narrow band gap, high absorption coefficient, high carrier mobility, realize organic battery carrier transport ability and the common lifting that solar spectrum absorbs.

Description

A kind of binary channels parallel connection type organic and inorganic based on first crystalline state porous nano germanium film Composite solar cell
Technical field
It is particularly a kind of based on first crystalline state porous nano germanium film the present invention relates to hybrid inorganic-organic solar cell Binary channels parallel connection type Organic-inorganic composite solar cell.
Technical background
Organic photovoltaic cell is referred to as the third generation solar cell, receives people's because of many advantages that its own possesses Extensive concern.Not only abundant raw materials, simple production process, cost are cheap and mutually simultaneous with flexible substrate for organic photovoltaic cell Hold, the production of large area can be carried out using volume to volume technology, thus with development and application prospect well.However, with nothing Machine battery is compared, and the current conversion efficiency of organic photovoltaic cell is relatively low, and the factor for restricting its conversion efficiency mainly have with It is lower 2 points：1）Polymeric material absorption spectrum mismatches with solar spectrum, causes organic battery relatively low to the utilization rate of sunshine, The short circuit current of device is not high；2）The carrier mobility of polymeric material is relatively low（~10-5cm2/V•s）, exciton diffusion length It is shorter（~10nm）, photogenerated charge is easy to compound.In addition, there is also spectral absorption and carrier collection mutually to make for organic battery About the problem of.In general, spectral absorption strengthens with the increase of absorber thickness, it is to be ensured that the enough light absorbs of battery are just To increase the thickness of absorbed layer as far as possible.But in organic battery, the diffusion length of exciton greatly limit active layer Thickness, the organic photovoltaic cell active layer thickness reported at present is commonly 100nm, will be increased greatly when thickness further increases Power-up and the recombination probability in hole, cause the deterioration of battery various performance parameters.
The it is proposed of hybrid inorganic-organic solar cell provides a good thinking for the solution of above mentioned problem.By nothing Machine nano material is introduced among organic battery as electron acceptor material, and inorganic material forms complementary light absorbs with organic material Meanwhile the characteristic of inorganic material high carrier mobility also compensate for the deficiency of the low carrier mobility of organic polymer.However, have Machine-current device performance of inorganic hybridization solar cell is also to be hoisted, and transformation efficiency and stability are all undesirable.
The content of the invention
The purpose of the present invention：For above-mentioned problem, invention is a kind of double based on first crystalline state porous nano germanium film Passage parallel connection type Organic-inorganic composite solar cell.
Technical scheme：Based on the bulk-heterojunction structure of organic photovoltaic cell donor/acceptor IPN, draw Enter a kind of first crystalline state porous nano germanium film with n-type conductive features, form organic donor/inorganic acceptors planar heterojunction knot Structure.In the composite construction that bulk-heterojunction and planar heterojunction coexist, realize that the binary channels carrier of parallel way is efficiently defeated Fortune.On the one hand, the specific surface area for improving germanium film of the combination high degree of loose structure and nano-scale, it is ensured that film Abundant contact with organic material and then form good organic/inorganic planar heterojunction.On the other hand, with non-crystalline material phase Than, first crystalline material has higher short range order parameter, while avoids high crystallization rate well again and bring grain boundary defects, because And there is good electric property.So the first crystalline state porous nano germanium film of n-type can be in organic donor/organic receptor body Electron transfer layer is used as in phase heterojunction structure, again can be in organic donor/inorganic acceptors planar heterojunction structure as inorganic Acceptor material, so as to the binary channels composite construction for building bulk-heterojunction and planar heterojunction coexists.Meanwhile narrow band gap, high suction The germanium material of coefficient, high carrier mobility is received by effective enhancing and the spectral absorption of expansion battery, and improves the current-carrying of battery Sub- transport capability, and then lift the performance of battery.In this battery, the first crystalline state porous nano germanium film of n-type uses capacity plate antenna Coupled plasma strengthens chemical vapor deposition（PECVD）System is prepared at ambient temperature, and the film is by size 5- 25nm germanium nano particle accumulation forms, as shown in Figure 1.Primary phase is to be in a kind of phase of amorphous phase and crystalline phase between the two Structure.The germanium nano particle of first crystalline state is by minimum germanium crystal grain（~1nm）Formed with the germanium cluster of shortrange order, as shown in Fig. 2 Due to the presence of these minimum crystal grain and orderly cluster, the SEAD of first crystalline state porous nano germanium film has substantially Donut feature.
A kind of described binary channels parallel connection type Organic-inorganic composite sun electricity based on first crystalline state porous nano germanium film Pond, its on a glass substrate preparation order be（As shown in Figure 3）：" 1 " is the first tin indium oxide（ITO）Transparency conducting layer, " 2 " It is zinc oxide（ZnO）Electron transfer layer, " 3 " are that porous nano germanium film layer, " 4 " are PTB7-Th and PC70BM is blended organic Layer, " 5 " are molybdenum oxides（MoO3）Hole transmission layer, " 6 " are the second tin indium oxides（ITO）Transparency conducting layer.Wherein, electric transmission Layer and blending organic layer are prepared using spin-coating method, and porous nano germanium is using capacity plate antenna coupled plasma enhancing chemical vapor deposition Product（PECVD）Prepared by method, hole transmission layer and tin indium oxide（ITO）Transparency conducting layer is prepared using Vacuum sublimation.Institute The solar cell stated at work sunshine by the second tin indium oxide（ITO）Transparency conducting layer side is incident.
A kind of described binary channels parallel connection type Organic-inorganic composite sun electricity based on first crystalline state porous nano germanium film The specific transport mechanism in pond, its band arrangement and electronics and hole is as shown in Figure 4：It is different in organic donor/organic receptor body phase Matter junction structure（PTB7-Th:PC70BM systems）In, light-generated excitons are in PTB7-Th and PC70BM interfaces separate, and electronics passes through PC70BM/Ge/ZnO/ITO is transported at electrode, and nanometer germanium film serves as electron transfer layer effect, and hole is then led to by PTB7-Th Road transports and at tunnelling to electrode, so as to realize the separation of light induced electron and hole and collection（As shown in path " 1 " in Fig. 4）； In the planar heterojunction structure of organic donor/inorganic acceptors（PTB7-Th:Ge systems）In, Ge particle is as electron acceptor Material, light-generated excitons are in PTB7-Th:Ge interfaces are separated, and electronics is transported at electrode by Ge/ZnO/ITO, and hole then passes through PTB7-Th passages transport and at tunnelling to electrode, equally realize the separation and collection in light induced electron and hole（Such as path in Fig. 4 Shown in " 2 "）.Bulk-heterojunction coexists with planar heterojunction, and binary channels independently carries out carrier transport, realizes the efficient defeated of parallel connection Fortune, its equivalent parallel circuit are as shown in Figure 5.
Beneficial effects of the present invention：It is proposed a kind of Organic-inorganic composite that bulk-heterojunction and planar heterojunction coexist too Positive electricity pond, the combination of the bulk-heterojunction of organic donor/organic receptor IPN and the planar heterojunction of organic donor/inorganic acceptors The common lifting of organic battery carrier transport and spectral absorption is realized, new thinking and side are provided for the development of organic battery To.
Brief description of the drawings
Fig. 1 is the surface SEM photograph of the first crystalline state porous nano germanium film of n-type conductive features.
Fig. 2 is the TEM and SEAD photo of the first crystalline state porous nano germanium film of n-type conductive features.
Fig. 3 is a kind of binary channels parallel connection type Organic-inorganic composite solar cell based on first crystalline state porous nano germanium film Structural representation.
Fig. 4 is a kind of binary channels parallel connection type Organic-inorganic composite solar cell based on first crystalline state porous nano germanium film Can band arrange and electronics and the transport mechanism schematic diagram in hole.
Fig. 5 is a kind of binary channels parallel connection type Organic-inorganic composite solar cell based on first crystalline state porous nano germanium film Equivalent parallel circuit diagram.
Embodiment
A kind of system of the binary channels parallel connection type Organic-inorganic composite solar cell based on first crystalline state porous nano germanium film Standby, detailed process is as follows：
1. glass substrate is cleaned by ultrasonic through electronics cleaning fluid/deionized water/alcohol/deionized water successively, nitrogen drying, adopt A layer thickness 100nm tin indium oxide is deposited with thermal evaporation deposition（ITO）Transparency conducting layer.
2. a pair above-mentioned deposition has tin indium oxide（ITO）The glass substrate of transparency conducting layer carries out 15min ozone processing, afterwards Spin coating a layer thickness is 30nm zinc oxide（ZnO）Electron transfer layer, and carry out 200 DEG C of annealing and handle for one hour.
3. the above-mentioned substrate through 200 DEG C of annealings enters capacity plate antenna coupled plasma enhancing chemical vapor deposition （PECVD）System, uses radio-frequency power supply of the frequency for 13.56MHz, and substrate and reaction chamber temperature maintain room temperature, be passed through germanium Alkane（GeH4）And hydrogen（H2）The percentage that the reacting gas of mixing, wherein germane account for volumetric flow of gas is 1%.Glow power It is set as 80W, electrode spacing is adjusted to 5cm, starts aura, aura 12min deposition of thick when chamber pressure stabilization is in 3.0Tor Spend for crystalline state porous nano germanium film at the beginning of 45nm n-type.
4. above-mentioned substrate strengthens chemical vapor deposition from capacity plate antenna coupled plasma（PECVD）System is taken out, by matter Amount is than being 1:1.5 PTB7-Th:PC70The uniform drop coating of BM blend solutions is in the substrate with crystalline state porous nano germanium film at the beginning of n-type On, after standing 35 seconds, 800 revs/min and 2000 revs/min rotate 10s and 60s respectively, are put into solvent anneal in culture dish 30min。
5. 5nm molybdenum oxide is sequentially depositing using thermal evaporation deposition（MoO3）The tin indium oxide of hole transmission layer and 100nm （ITO）Transparency conducting layer and silver grating line electrode, so far prepared by battery to complete.

Claims (2)

  1. A kind of 1. application of the first crystalline state porous nano germanium film material with n-type conductive features, it is characterised in that：The nanometer Germanium film is formed by particle packing, particle size 5-25nm, by the nanometer germanium film be used for binary channels parallel connection type it is organic-nothing Machine composite solar cell, the solar cell use organic donor/organic receptor bulk-heterojunction and organic donor/inorganic acceptors The composite construction that planar heterojunction coexists, the composite construction realizes the binary channels carrier transport of parallel way, described organic Donor/organic receptor bulk-heterojunction is by PTB7-Th and PC70BM form, the organic donor/inorganic acceptors planar heterojunction by PTB7-Th and porous nano germanium film composition, porous nano germanium film is as organic donor/organic receptor bulk-heterojunction structure Electron transfer layer, while as the inorganic acceptors material of organic donor/inorganic acceptors planar heterojunction structure, organic donor/ Organic receptor bulk-heterojunction and organic donor/inorganic acceptors planar heterojunction are formed simultaneously in a spin coating proceeding, specifically Method is as follows：It is 1 by mass ratio:1.5 PTB7-Th:PC70The uniform drop coating of BM blend solutions is quiet on porous nano germanium film After putting 35s, 10s and 60s is rotated respectively at 800 revs/min and 1500 revs/min.
  2. 2. the application of the first crystalline state porous nano germanium film material with n-type conductive features as claimed in claim 1, its feature It is：The solar cell is prepared as：The first indium tin oxide transparent conductive layer, zinc oxide electricity are sequentially formed on a glass substrate Sub- transport layer, porous nano germanium film layer, PTB7-Th and PC70Organic layer, molybdenum oxide hole transmission layer, the second oxygen of BM blendings Change indium tin transparency conducting layer, the thickness of the first indium tin oxide transparent conductive layer and the second indium tin oxide transparent conductive layer is 100nm, the thickness of the zinc oxide electron transfer layer is 30nm, and the porous nano germanium film thickness degree is 45nm, described PTB7-Th and PC70The thickness of the organic layer of BM blendings is 100nm, and the thickness of the molybdenum oxide hole transmission layer is 5nm, described Sunshine is incident by the second indium tin oxide transparent conductive layer side at work for solar cell.
CN201610167336.6A 2016-03-23 2016-03-23 A kind of binary channels parallel connection type organo-mineral complexing solar cell based on first crystalline state porous nano germanium film Expired - Fee Related CN105591031B (en)

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CN108447991A (en) * 2018-03-21 2018-08-24 南开大学 A kind of binode hybrid solar cell in parallel based on inorganic nano-crystal
CN109256468A (en) * 2018-07-31 2019-01-22 中国科学院合肥物质科学研究院 A kind of hydridization solar cell and preparation method thereof integrated based on a variety of hetero-junctions performances

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CN101736321A (en) * 2009-12-17 2010-06-16 南开大学 Method for preparing microcrystalline silicon-germanium film by adopting helium-hydrogen gas mixing and diluting method
CN103296209A (en) * 2013-05-29 2013-09-11 中国科学院半导体研究所 Solar cell combining heterostructure plasmons and bulk heterojunctions

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