CN106953014A - A kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer - Google Patents
A kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer Download PDFInfo
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- CN106953014A CN106953014A CN201710210648.5A CN201710210648A CN106953014A CN 106953014 A CN106953014 A CN 106953014A CN 201710210648 A CN201710210648 A CN 201710210648A CN 106953014 A CN106953014 A CN 106953014A
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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- 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
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Abstract
The present invention relates to one kind with hybrid solar cell of the CuPc (CuPc) for hole transmission layer.Organic inorganic hybridization solar cell of the present invention includes transparent conductive substrate, copper phthalocyanine hole transport layer, CH successively from down to up3NH3PbX3（X is Cl, I or their mixing in formula）Organic inorganic hybridization perovskite photosensitive layer, electron transfer layer and reflecting electrode composition.Advantages and positive effects of the present invention：In hybrid solar cell, there is good film forming characteristics and preferable cavity transmission ability using CuPc as hole transmission layer, the compound of electron-hole has obtained effective suppression, and photoelectric transformation efficiency is higher；CuPc gets a promotion as hole transmission layer, stable chemical nature, device lifetime；Device preparation method technique is simple, reaction temperature is low, efficiency high, abundant raw materials, low cost, suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to a kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer, category
In thin-film material and devices field.
Background technology
In recent years, in order to solve the increasingly serious energy and environmental problem, people have invested sight the exploitation of new energy
It is upper with utilizing.In various new energy technologies, solar power generation is undoubtedly one of most promising direction.Traditional silicon substrate is too
Although positive energy battery realizes industrialization, there is more ripe market, but its cost performance can not also mutually be competed with traditional energy,
And the pollution and energy consumption problem in manufacturing process have impact on its extensive use.Therefore, research and development high efficiency, low cost
Novel solar battery is very necessary.In numerous novel solar batteries, the de- grain husk of nearly 2 years of perovskite solar cell and
Go out, since PARK seminars in 2012 report that more than 500 hours life-span, efficiency reach the 9.7% all solid state perovskite sun first
Since energy battery, perovskite solar cell receives the very big concern of educational circles and industrial circle, quickly grows, goes back quilt
《Science》It is chosen as one of ten big sciences breakthrough in 2013.
Perovskite solar cell has the advantages that the big absorption coefficient of light, exciton diffusion length length, carrier mobility are high.
The structure of typical perovskite solar cell has two kinds：One kind is meso-hole structure, and another is planar structure.With meso-hole structure
Compare, planar structure perovskite battery structure is simple, can prepare under cryogenic.Plane perovskite solar cell be exactly
The front and rear of perovskite photosensitive layer forms sandwich structure plus electron transfer layer and hole transmission layer respectively.In plane perovskite too
The use of most hole mobile material is Poly (3,4-ethylene dioxythiophene) in positive energy battery: poly
(styrene sulfonate) (PEDOT:PSS) .Although using PEDOT:PSS as hole transmission layer perovskite battery
Higher efficiency can be reached, but is due to PEDOT:PSS has certain acidity, its ITO or FTO electrodes can be produced compared with
Strong corrosiveness, causes the decline of device lifetime.Therefore exploitation transmission performance is good, and hole transmission layer stable in properties very must
Will.
CuPc (CuPc) is a kind of highly stable phthalocyanine metal compound of property, and synthetic method is simple, cheap
Possesses excellent photoelectric functional characteristic.CuPc advantageous property make it that it is widely applied in numerous areas.Profit
The liquid crystal light valve of function admirable can be prepared with its photoconduction.Sensitive gas sensing can be prepared using its gas sensing property
Device.Because CuPc photovoltaic effect and good cavity transmission ability can prepare stable, cheap solar cell of performance etc.
Deng.Due to CuPc one side stable chemical natures, water insoluble, alcohol, on the other hand, its cavity transmission ability are excellent, its HOMO
Energy level is 5.2 eV or so, and the HOMO level-density parameters with conventional organic inorganic hybridization perovskite material are good, can accelerate sky
The collection in cave, reduces the compound of electronics and hole.The present invention is exactly the advantage for the these two aspects that make use of CuPc, is on the one hand improved
The efficiency of organic-inorganic perovskite solar cell, on the other hand improves its working life.At present, also not in organic inorganic hybridization
The relevant report for using CuPc as hole transmission layer is seen in perovskite solar cell.
The content of the invention
Hybrid solar cell the present invention relates to one kind using CuPc (CuPc) as hole transmission layer.For existing skill
The deficiency of art, it is therefore intended that a kind of CuPc is provided and is used as perovskite solar cell of hole transmission layer and preparation method thereof
To achieve the above object, the technical solution adopted in the present invention is:A kind of is hole transmission layer with CuPc (CuPc)
Hybrid solar cell, it is characterised in that include transparent conductive substrate, CuPc hole transmission layers, You Jiwu successively from down to up
Machine hydridization perovskite photosensitive layer, electron transfer layer and reflecting electrode.
In such scheme, described transparent conductive substrate has ITO, FTO, AZO glass substrate or flexible liner for deposition
Bottom.
In such scheme, using CuPc as hole transmission layer, thickness of hole transport layer 20-50 nm.
In such scheme, organic inorganic hybridization perovskite photosensitive layer is CH3NH3PbX3（In formula X be Cl, I or they
Mixture）, CH3NH3PbX3Photosensitive layer thickness is 100-1000 nm.
In such scheme, described electron transfer layer is two-layer composite, including the first electron transfer layer and the second electricity
Sub- transport layer；Wherein, the first electron transfer layer is C60、C70, one kind in PCBM, the first electron transfer layer thickness is 30-50
nm；Second electron transfer layer is Bphen, BCP, AlQ3In one kind, thickness is in 5-10 nm.
In such scheme, described reflecting electrode is one kind in Al electrodes, Ag electrodes, Au electrodes, the reflecting electrode
Thickness be 80-200 nm.
In such scheme, the preparation of device comprises the following steps：
(1) transparent substrates are pre-processed：Transparent substrates are cleaned successively using acetone, glass cleaner, then in acetone, deionization
Each ultrasonically treated 10 minutes in water, isopropanol, after being dried up with nitrogen ultra violet lamp handle 10 minutes it is stand-by；
(2) prepared by hole transmission layer：In vacuum coating equipment, vacuum is less than 5 × 10-4Vacuum condition under, in transparent substrates
The CuPc layers that the upper method by thermal evaporation deposits one layer of 20-50 nm are used as hole transmission layer；Film thickness passes through quartz crystal oscillator
Piece is monitored, and sedimentation rate is controlled in 0.05-0.1 nm/s；
(3) prepared by organic inorganic hybridization perovskite photosensitive layer：Organic inorganic hybridization perovskite precursor solution is configured at room temperature,
By quantitative CH3NH3I, PbX2 (X is I, Cl) dissolve in DMF (DMF), and heating 12 is small under the conditions of 60 DEG C
It is abundant up to dissolving, obtain organic inorganic hybridization perovskite precursor solution；Using sol evenning machine by precursor solution rotary coating
On hole transmission layer；Made annealing treatment 10-120 minutes in 100 DEG C of heating plate, remove residual solvent and crystal property is made
Good organic inorganic hybridization perovskite photosensitive layer；
(4) electron transfer layer is prepared：In CH3NH3PbX3Given birth on organic inorganic hybridization perovskite photosensitive layer by the method for thermal evaporation
Long 30-100 nm C60(or C70) or the 30-100 nm PCBM of spin coating method growth be used as the first electric transmission
Layer；Continue vacuum thermal evaporation 5-10 nm Bphen, BCP, AlQ3In a kind of be used as the second electron transfer layer to complete electronics to pass
The preparation of defeated layer.
(5) reflecting electrode is prepared：On the electron transport layer by the method for thermal evaporation deposit one layer of 80-200 nm Al,
Ag or Au completes the preparation of hybrid solar cell as reflecting electrode.
Beneficial effects of the present invention are as follows：CuPc hole transmission layers prepared by the present invention at least have the effect that:(1)
The collection in hole can be promoted, suppress the compound of electron hole, improve the energy conversion efficiency of device;(2) due to CuPc's
Stable chemical nature, to CH3NH3PbX3Organic inorganic hybridization perovskite photosensitive layer and transparency electrode possess certain protective effect,
Avoid acid PEDOT simultaneously:PSS use, improves device lifetime.(3) the CuPc hole transmission layers described in can be using existing
Prepared by the disposable evaporation film-forming of some evaporated devices, simple to operate, with low cost, be easily achieved large area production.
Brief description of the drawings
Fig. 1 is the hybrid solar cell structural representation using CuPc as hole transmission layer of the present invention.
Embodiment
It is a kind of with the hybrid solar cell that CuPc (CuPc) is hole transmission layer, device architecture is：Electrically conducting transparent is served as a contrast
Bottom/CuPc hole transmission layers/organic inorganic hybridization perovskite photosensitive layer/electron transfer layer/reflecting electrode, with reference to specific
Embodiment the present invention is described in further detail.
Embodiment one
A kind of hybrid solar cell using CuPc as hole transmission layer, using CuPc as the hole transmission layer of battery, tool
The device architecture of body is：ITO/CuPc (20 nm)/ CH3NH3PbI3 (200 nm)/C60 (50 nm)/Bphen (5 nm)/
Ag (100 nm), wherein ITO are used as hole transmission layer, 200 nm as transparent conductive substrate, 20 nm CuPc
CH3NH3PbI3It is used as organic inorganic hybridization perovskite photosensitive layer, 50 nm C60Transmitted with 5 nm Bphen as composite electron
Layer, 100 nm Ag is used as reflecting electrode.The preparation of device includes step in detail below.
The first step：Substrate is cleaned；
Transparent substrate is cleaned successively using acetone, glass cleaner, each ultrasonically treated 10 in acetone, deionized water, isopropanol
Minute, ultra violet lamp is handled 10 minutes after nitrogen drying.
Second step：CuPc hole transmission layers are deposited；
In vacuum coating equipment, vacuum is less than 5 × 10-4Vacuum condition under, sunk on a transparent substrate by the method for thermal evaporation
One layer of 20 nm of product CuPc is used as hole transmission layer；Film thickness is monitored by quartz crystal, and sedimentation rate is controlled 0.05
nm/s。
3rd step：It is prepared by organic inorganic hybridization perovskite photosensitive layer：Organic inorganic hybridization perovskite forerunner is configured at room temperature
Liquid solution, by 0.8 g CH3NH3I and 2.3 g PbI2Dissolved in 15.8 ml DMF (DMF), 60
12 hours are heated under the conditions of DEG C to dissolving fully, organic inorganic hybridization perovskite precursor solution is obtained；Using sol evenning machine by before
Liquid solution rotary coating is driven on hole transmission layer, rotating speed is 3000rpm, the time is 30 seconds；Then in 100 DEG C of heating plate
Annealing 60 minutes, removes residual solvent and the good CH of crystal property is made3NH3PbI3Organic inorganic hybridization perovskite light
Photosensitive layer.
4th step：Electron transfer layer is prepared on perovskite photosensitive layer；Ultra high vacuum deposition system is opened, loading grows
CH3NH3PbI3The substrate and electron transport layer materials C of perovskite photosensitive layer60；It is small that ultra high vacuum deposition system is evacuated to pressure
In 10-4After Pa, start vacuum moulding machine C60/ Bphen electron transfer layers；The thickness of electron transfer layer is monitored using quartz crystal,
First deposit C60First electron transfer layer, C60Thickness is in 50 nm.Then in C60Continue to deposit 5 nm on first electron transfer layer
Bphen layers are used as the second electron transfer layer；Sedimentation rate is controlled in 0.1 nm/s.
5th step：100 nm Ag are deposited on electron transfer layer as reflecting electrode, the nm/s of sedimentation rate 0.5, device system
It is standby to complete.
6th step：Test；Solar energy test is carried out to device under AM1.5 simulated solar irradiations, acquisition is made with CuPc
Solar energy parameter for the organic inorganic hybridization perovskite solar cell of hole transmission layer is short circuit current flow 18.2/cm2, open circuit
Voltage 0.92, fill factor, curve factor 0.69, energy conversion efficiency 11.5%.Stored 3 months under dark condition, device efficiency is maintained just
The 83% of beginning efficiency.With PEDOT:PSS is deposited under dark condition as the comparative device energy conversion efficiency 11.2% of hole transmission layer
After storage 3 months, device energy conversion efficiency only has 0.9%, and less than the 10% of starting efficiency, this turns out the organic inorganic hybridization sun
Energy battery can use CuPc as hole transmission layer really, while CuPc can also greatly improve device as hole transmission layer
Life-span.
Embodiment two
A kind of hybrid solar cell using CuPc as hole transmission layer, is passed using CuPc (CuPc) as the hole of battery
Defeated layer, specific device architecture is：ITO/CuPc (50 nm)/ CH3NH3PbIXCl3-X (300 nm)/C70 (30 nm)/BCP
(10 nm)/Al (200 nm), wherein ITO are used as hole transmission layer, 300 nm as transparent conductive substrate, 50 nm CuPc
CH3NH3PbIXCl3-XIt is used as organic inorganic hybridization perovskite photosensitive layer, 30 nm C70Passed with 10 nm BCP as composite electron
Defeated layer, 200 nm Al is used as reflecting electrode.The preparation of device includes step in detail below.
The first step：Substrate is cleaned；
Be the same as Example one
Second step：CuPc hole transmission layers are deposited；
In vacuum coating equipment, vacuum is less than 5 × 10-4Vacuum condition under, sunk on a transparent substrate by the method for thermal evaporation
One layer of 50 nm of product CuPc is used as hole transmission layer；Film thickness is monitored by quartz crystal, and sedimentation rate is controlled 0.1
nm/s。
3rd step：It is prepared by organic inorganic hybridization perovskite photosensitive layer：Organic inorganic hybridization perovskite forerunner is configured at room temperature
Liquid solution, using DMF as solvent, configures CH3NH3I and PbCl2Mol ratio is 3：1 perovskite precursor solution, 60 DEG C of conditions
Lower heating is extremely dissolved abundant for 12 hours；Using sol evenning machine by precursor solution rotary coating on CuPc hole transmission layers, rotating speed
For 2500 rpm, the time is 40 seconds；Then made annealing treatment 90 minutes in 100 DEG C of heating plate, remove residual solvent and be made
The good CH of crystal property3NH3PbIXCl3-XOrganic inorganic hybridization perovskite photosensitive layer.
4th step：Electron transfer layer is prepared on perovskite photosensitive layer；Ultra high vacuum deposition system is opened, loading grows
CH3NH3PbI3The substrate and electron transport layer materials C of perovskite photosensitive layer70；It is small that ultra high vacuum deposition system is evacuated to pressure
In 10-4After Pa, start vacuum moulding machine C70/ BCP electron transfer layers；The thickness of electron transfer layer is monitored using quartz crystal, first
Deposit C70First electron transfer layer, C70Thickness is in 30 nm.Then in C60Continue to deposit 10 nm BCP on first electron transfer layer
Layer is used as the second electron transfer layer；Sedimentation rate is controlled in 0.05 nm/s.
5th step：200 nm Al are deposited on electron transfer layer as reflecting electrode, the nm/s of sedimentation rate 0.5, device system
It is standby to complete.
6th step：Test；Solar energy test is carried out to device under AM1.5 simulated solar irradiations, acquisition is made with CuPc
Solar energy parameter for the organic inorganic hybridization perovskite solar cell of hole transmission layer is short circuit current flow 20.1/cm2, open circuit
Voltage 0.91, fill factor, curve factor 0.67, energy conversion efficiency 12.2%.Stored 3 months under dark condition, device efficiency is maintained just
The 79% of beginning efficiency.Illustrate CuPc can as hybrid solar cell hole transmission layer, and device possesses higher energy
Conversion efficiency and life-span.
Claims (7)
1. a kind of hybrid solar cell using CuPc as hole transmission layer, it is characterised in that include successively from down to up
Transparent conductive substrate, copper phthalocyanine hole transport layer, organic inorganic hybridization perovskite photosensitive layer, electron transfer layer and reflecting electrode.
2. a kind of hybrid solar cell using CuPc as hole transmission layer as claimed in claim 1, it is characterised in that
Described transparent conductive substrate has ITO, FTO, AZO glass substrate or flexible substrate for deposition.
3. a kind of hybrid solar cell using CuPc as hole transmission layer as claimed in claim 1, it is characterised in that
Described solar cell uses CuPc as hole transmission layer, thickness of hole transport layer 20-50 nm.
4. a kind of hybrid solar cell using CuPc as hole transmission layer as claimed in claim 1, it is characterised in that
Described organic inorganic hybridization perovskite photosensitive layer CH3NH3PbX3（X is Cl, I or their mixing in formula）, CH3NH3PbX3
Photosensitive layer thickness is 100-1000 nm.
5. a kind of hybrid solar cell using CuPc as hole transmission layer as claimed in claim 1, it is characterised in that
Described electron transfer layer is two-layer composite, including the first electron transfer layer and the second electron transfer layer；Wherein, the first electricity
Sub- transport layer is C60、C70, one kind in PCBM, the first electron transfer layer thickness is 30-50 nm；Second electron transfer layer is
Bphen、BCP、AlQ3In one kind, thickness is in 5-10 nm.
6. a kind of hybrid solar cell using CuPc as hole transmission layer as claimed in claim 1, it is characterised in that institute
The reflecting electrode stated is one kind in Al electrodes, Ag electrodes, Au electrodes, and the thickness of the reflecting electrode is 80-200 nm.
7. a kind of preparation method using CuPc as the hybrid solar cell of hole transmission layer as claimed in claim 1, its
It is characterised by, the preparation of device comprises the following steps：
(1) transparent substrates are pre-processed：Transparent substrates are cleaned successively using acetone, glass cleaner, then in acetone, deionization
Each ultrasonically treated 10 minutes in water, isopropanol, after being dried up with nitrogen ultra violet lamp handle 10 minutes it is stand-by；
(2) prepared by hole transmission layer：Vacuum is less than 5 × 10-4Vacuum condition under, pass through thermal evaporation on a transparent substrate
The phthalocyanine layers of copper that method deposits one layer of 20-50 nm is used as hole transmission layer；Film thickness is monitored by quartz crystal, deposition
Speed control is in 0.05-0.1 nm/s；
(3) prepared by organic inorganic hybridization perovskite photosensitive layer：Organic inorganic hybridization perovskite precursor solution is configured at room temperature,
By quantitative CH3NH3I、PbX2(X is I, Cl, Br) is dissolved in DMF (DMF), and 12 are heated under the conditions of 60 DEG C
Hour is abundant to dissolving, and obtains organic inorganic hybridization perovskite precursor solution；Precursor solution is rotated using sol evenning machine and applied
Overlay on hole transmission layer；Make annealing treatment 10-120 minutes on hot plate, remove residual solvent and obtained crystal property is good
Organic inorganic hybridization perovskite photosensitive layer；
(4) electron transfer layer is prepared：30-100 is grown by the method for thermal evaporation on organic inorganic hybridization perovskite photosensitive layer
Nm C60(or C70) or the 30-100 nm PCBM of spin coating method growth be used as the first electron transfer layer；Continue vacuum
Hot evaporation 5-10 nm Bphen, BCP, AlQ3In a kind of preparation for being used as the second electron transfer layer, completing electron transfer layer；
(5) reflecting electrode is prepared：On the electron transport layer by the method for thermal evaporation deposit one layer of 80-200 nm Al, Ag or
Person Au completes the preparation of hybrid solar cell as reflecting electrode.
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| CN107611267A (en) * | 2017-09-07 | 2018-01-19 | 济南大学 | A kind of construction method of flexible wearable paper substrate perovskite solar cell |
| CN107863443A (en) * | 2017-10-17 | 2018-03-30 | 华中科技大学 | A kind of flexible transconfiguration perovskite solar cell and preparation method thereof |
| CN108625517A (en) * | 2018-03-23 | 2018-10-09 | 武汉理工大学 | A kind of energy-saving power generating glass curtain wall based on transparent perovskite photovoltaic module |
| CN108859679A (en) * | 2018-03-23 | 2018-11-23 | 武汉理工大学 | A kind of energy-saving power generating vehicle glass based on transparent perovskite photovoltaic module |
| CN112349843A (en) * | 2020-11-06 | 2021-02-09 | 中国科学技术大学 | Hole transport layer material of solar cell, antimony-based solar cell and preparation method of antimony-based solar cell |
| CN113285028A (en) * | 2021-04-22 | 2021-08-20 | 北方民族大学 | Perovskite solar cell manufacturing method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611267A (en) * | 2017-09-07 | 2018-01-19 | 济南大学 | A kind of construction method of flexible wearable paper substrate perovskite solar cell |
| CN107863443A (en) * | 2017-10-17 | 2018-03-30 | 华中科技大学 | A kind of flexible transconfiguration perovskite solar cell and preparation method thereof |
| CN108625517A (en) * | 2018-03-23 | 2018-10-09 | 武汉理工大学 | A kind of energy-saving power generating glass curtain wall based on transparent perovskite photovoltaic module |
| CN108859679A (en) * | 2018-03-23 | 2018-11-23 | 武汉理工大学 | A kind of energy-saving power generating vehicle glass based on transparent perovskite photovoltaic module |
| CN112349843A (en) * | 2020-11-06 | 2021-02-09 | 中国科学技术大学 | Hole transport layer material of solar cell, antimony-based solar cell and preparation method of antimony-based solar cell |
| CN112349843B (en) * | 2020-11-06 | 2022-09-06 | 中国科学技术大学 | Hole transport layer material of solar cell, antimony-based solar cell and preparation method of antimony-based solar cell |
| CN113285028A (en) * | 2021-04-22 | 2021-08-20 | 北方民族大学 | Perovskite solar cell manufacturing method |
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| CN106953014B (en) | 2020-07-03 |
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