CN110311037A - A kind of flexibility perovskite hole transmission layer used for solar batteries and its preparation method and application - Google Patents
A kind of flexibility perovskite hole transmission layer used for solar batteries and its preparation method and application Download PDFInfo
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- CN110311037A CN110311037A CN201910550777.8A CN201910550777A CN110311037A CN 110311037 A CN110311037 A CN 110311037A CN 201910550777 A CN201910550777 A CN 201910550777A CN 110311037 A CN110311037 A CN 110311037A
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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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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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Abstract
The invention belongs to perovskite technical field of solar batteries, more particularly to a kind of preparation method of flexible perovskite hole transmission layer used for solar batteries, include: to mix PEDOT:PSS solution with organic cosolvent, the first preset time is handled under 0~10 DEG C of cryogenic conditions, obtains spin coating liquid；Also flexible conducting substrate is placed in spin coating instrument and carries out low-temperature treatment, the temperature of the low-temperature treatment is -5~5 DEG C；Spin coating drop is added to and carries out spin coating on flexible conducting substrate, the flexible conducting substrate for loading PEDOT:PSS taking-up is placed on warm table after spin coating and is thermally dried, flexibility perovskite hole transmission layer used for solar batteries is made.The defects of the present invention prepares the PEDOT:PSS hole transmission layer of quasi- condensation using low-temperature treatment spin coating, significantly improve the water vapor erosiveness and electric conductivity of hole transmission layer, and reduce hole transmission layer.
Description
Technical field
The invention belongs to perovskite technical field of solar batteries, and in particular to a kind of flexibility perovskite is used for solar batteries
Hole transmission layer and its preparation method and application.
Background technique
As the whole world is stepped up energy demand, the non-renewable energy resources such as the only petroleum of the earth, coal mine will be
Soon future is consumed totally.So Renewable Energy Development is significant and far-reaching.In different new energy technologies
In, environment amenable solar battery technology is prioritized.The development and extensive use of new material and new technology are the sun
Energy battery industry continuously infuses new blood.
Perovskite solar cell (Perovskite solar cells, PSCs) is because having both simple solution preparation, efficiently
Rate and be concerned, highest photoelectric conversion efficiency is more than 24% at present.Perovskite solar battery is prepared most basic and is answered
It is spin-coating method with a kind of most wide method, using spin coating instrument by hole transmission layer, calcium titanium ore bed and electron transfer layer successively spin coating
In conductive substrates, finally plates metal electrode and just successfully prepare easy perovskite solar battery.It is conductive by connection
The circuit of substrate and metal electrode and generate photoelectric current.In various solar batteries, advantage of lower cost and easily made of it is soft
Property perovskite solar battery has attracted extensive concern.In perovskite solar battery, calcium titanium ore bed is core, usually
By CH3NH3PbI3It constitutes.In order to optimize perovskite solar battery, thin film-forming method and membrance casting condition to calcium titanium ore bed are carried out
Extensive and in-depth research.PEDOT:PSS is widely used in perovskite solar battery as hole transmission layer, with obtain by
In almost without it is sluggish, can low temperature preparation, be suitble to prepare flexible device.However, the low conductivity of PEDOT:PSS and hygroscopic etc. asking
Topic, is greatly reduced the photoelectric conversion efficiency of perovskite battery.In order to solve this problem, researchers have done many trials, such as:
The reference of cosolvent, dopamine modification by copolymerization carry out post-processing to PEDOT:PSS using aqueous methanol and other mix, close
At, catalysis the methods of.In the above method, introduces organic cosolvent and be acknowledged as the most effective means.However, due to having
The quantitative limitation of molecular linkage point is imitated, cosolvent method is still limited to the promotion effect of conductivity.
Summary of the invention
Based on the above deficiencies in the existing technologies, it is used for solar batteries that the present invention provides a kind of flexible perovskite of raising
The method of hole transmission layer performance.
In order to achieve the above object of the invention, the invention adopts the following technical scheme:
A kind of preparation method of flexibility perovskite hole transmission layer used for solar batteries, comprising the following steps:
(1) PEDOT:PSS solution is mixed with organic cosolvent, it is default that first is handled under 0~10 DEG C of cryogenic conditions
Time obtains spin coating liquid；Also flexible conducting substrate is placed in spin coating instrument and carries out low-temperature treatment, the temperature of the low-temperature treatment
It is -5~5 DEG C；
(2) spin coating drop is added to and carries out spin coating on flexible conducting substrate, the flexibility of PEDOT:PSS will be loaded after spin coating
Conductive substrates taking-up, which is placed on warm table, to be thermally dried, and flexibility perovskite hole transmission layer used for solar batteries is made.
Preferably, the volume ratio of the PEDOT:PSS solution and organic cosolvent is (20~30): 1.
Preferably, the organic cosolvent is isopropanol, DMSO or DMF.
Preferably, first preset time is 1~20 hour.
Preferably, it is 3000~6000 revs/min that the condition of the spin coating, which includes: revolving speed, and the time is 10~60
Second, relative humidity 10~90%.
Preferably, the relative humidity is 50%.
Preferably, it is 90~150 DEG C that the condition of the heat drying, which includes: heating temperature, heating time 10
~90 minutes.
The present invention also provides a kind of flexible perovskite hole transmission layers used for solar batteries, as described in either a program as above
Preparation method is made.
The present invention also provides the application of flexible perovskite hole transmission layer used for solar batteries, the hole transmission layer and calcium
The flexible perovskite solar battery of the compound composition of titanium ore layer, electron transfer layer, metal electrode.
Compared with prior art, the present invention beneficial effect is:
The present invention prepares the PEDOT:PSS hole transmission layer of quasi- condensation using low-temperature treatment spin coating, significantly improves hole biography
The defects of the water vapor erosiveness and electric conductivity of defeated layer, and reduce hole transmission layer；It is as perovskite solar energy as a result,
When the hole transmission layer of battery, flexible perovskite solar-electricity can be prepared in high humidity environment under conditions of being not necessarily to glove box
Pond, and efficiency, humidity-proof ability and the stability of corresponding perovskite solar battery is made to be improved significantly.
Detailed description of the invention
Fig. 1 is the flow chart of spin coating liquid spin-coating film on flexible conducting substrate of the embodiment of the present invention；
Fig. 2 is the scanning electron microscope in the embodiment of the present invention in humidity for different hole transmission layers obtained under 70% environment
SEM photograph；Wherein, (a) the corresponding non-low-temperature treatment of spin coating liquid, (b) corresponding spin coating liquid passes through low-temperature treatment；
Fig. 3 be the embodiment of the present invention different humidity under the conditions of the forward and backward PEDOT:PSS film of low-temperature treatment conductivity；
It wherein, is non-low-temperature treatment before low-temperature treatment；
Fig. 4 be the embodiment of the present invention different humidity under the conditions of the forward and backward PEDOT:PSS film of low-temperature treatment roughness；
It wherein, is non-low-temperature treatment before low-temperature treatment；
Fig. 5 is the embodiment of the present invention when relative humidity is 70%, and the PEDOT:PSS of non-low-temperature treatment is passed as hole
The C-V characteristic that defeated layer and the PEDOT:PSS of low-temperature treatment are assembled into flexible perovskite solar battery as hole transmission layer is bent
Line chart；Wherein, interior illustration is the digital photograph of flexible battery.
Specific embodiment
In order to illustrate the embodiments of the present invention more clearly, Detailed description of the invention a specific embodiment of the invention will be compareed below.
Embodiment 1:
The preparation method of the flexible perovskite hole transmission layer used for solar batteries of the present embodiment, comprising the following steps:
Firstly, quasi- solidifying state (congealing) PEDOT:PSS solution is prepared, poly- (3,4- Ethylenedioxy Thiophene)-is poly-
(styrene sulfonic acid) solution (i.e. PEDOT:PSS solution) is mixed with isopropanol with the volume ratio of 20:1, then is handled under 5 DEG C of low temperature
8 hours；Clean flexible ITO/PET conductive substrates are placed under 0 DEG C of low temperature environment simultaneously；Then it is in envionmental humidity
PEDOT:PSS solution under conditions of 70% by quasi- condensation is added drop-wise in the flexible ITO/PET substrate under low temperature environment, uses rotation
Instrument spin coating is applied, revolving speed is 5000 revs/min, and the time is 30 seconds, as shown in Figure 1；Flexible ITO/PET substrate is put after spin coating
It sets and is heated in warm table, heating temperature is 120 DEG C, it heats 60 minutes, to obtain PEDOT in flexible ITO/PET substrate:
PSS film, i.e. hole transmission layer.
To assemble flexible perovskite solar battery, perovskite light-absorption layer is prepared on the hole transport layer, is prepared again later
Electron transfer layer；Finally, one layer of silver electrode is deposited on the electron transport layer, to obtain flexible perovskite solar cell device.
Fig. 2 be in the case where humidity is 70% environment it is obtained difference hole transmission layer scanning electron microscope (SEM) photos, wherein scheming
2 (a) for non-low-temperature treatment (room temperature, 20 DEG C) PEDOT:PSS made from hole transmission layer, Fig. 2 (b) be low-temperature treatment after have
Hole transmission layer made from the PEDOT:PSS of quasi- condensation state；Therefrom it can be found that the PEDOT of the quasi- condensation state after low-temperature treatment:
PSS film defects are few, more uniform.
Under the conditions of Fig. 3 and Fig. 4 is respectively different humidity, the conductivity of the forward and backward PEDOT:PSS film of low-temperature treatment and coarse
Degree；It can be found that after low-temperature treatment, the conductivity of hole transmission layer is significantly improved, and roughness in the case where humidity is 70% environment
It is decreased obviously.
Fig. 5 shows the flexible perovskite solar-electricity based on the forward and backward PEDOT:PSS hole transmission layer assembling of low-temperature treatment
Pond VA characteristic curve figure, interior illustration are battery digital photograph.Therefrom it can be found that the hole obtained after low-temperature treatment
The photoelectric conversion efficiency of the flexible perovskite solar battery of transport layer assembling has been more than 15.2%, the phase with non-low-temperature treatment
Than cell photoelectric transfer efficiency is doubled；This be attributed to by regulating and controlling temperature enhance cosolvent (isopropanol) and PSS it
Between HYDROGEN BOND INTENSITY.
Embodiment 2:
The present embodiment and embodiment one the difference is that: research different humidity is used for solar batteries to flexible perovskite
The performance of hole transmission layer influences.
Specifically, the preparation method is the same as that of Example 1 for flexible perovskite hole transmission layer used for solar batteries, only in difference
Humidity environment under studied.As shown in Fig. 3 and Fig. 4 in embodiment 1, it is found that the hole transport after low-temperature treatment
Hole transmission layer of the layer relative to non-low-temperature treatment, conductivity significantly improves, and roughness is decreased obviously；In addition, humidity
Variation influences the conductivity of the hole transmission layer after low-temperature treatment and roughness smaller；And the variation of humidity is to non-low temperature
The conductivity and roughness of the hole transmission layer of processing are affected.Thus illustrate, the PEDOT:PSS film after low-temperature treatment
Humidity stability is preferable.
In addition, the light of the flexible perovskite solar battery assembled based on PEDOT:PSS hole transmission layer after low-temperature treatment
Photoelectric transformation efficiency is all higher than flexible perovskite solar battery corresponding with non-low-temperature treatment, improves about 20~100%.And
And under the conditions of relative humidity 50%, the photoelectric conversion efficiency highest of battery, about 17.7%.
Embodiment 3:
The preparation method of the flexible perovskite hole transmission layer used for solar batteries of the present embodiment, comprising the following steps:
Firstly, preparing quasi- solidifying state PEDOT:PSS solution；PEDOT:PSS solution and isopropanol are mixed with the volume ratio of 20:1
It closes, then is handled 20 hours under 10 DEG C of low temperature；Clean flexible ITO/PET conductive substrates are placed on -5 DEG C of low temperature environments simultaneously
Under；Then under the PEDOT:PSS solution of quasi- condensation being added drop-wise to low temperature environment under conditions of envionmental humidity is 90%
In flexible ITO/PET substrate, using spin coating instrument spin coating, revolving speed is 6000 revs/min, and the time is 60 seconds, spin coating process and implementation
Example 1 is similar；Flexible ITO/PET substrate is placed on warm table heating after spin coating, heating temperature is 150 DEG C, heats 10 points
Clock, to obtain PEDOT:PSS film, i.e. hole transmission layer on a flexible substrate.
To assemble flexible perovskite solar battery, perovskite light-absorption layer is prepared in hole transport, prepares electricity again later
Sub- transport layer；Finally, one layer of silver electrode is deposited on the electron transport layer, to obtain flexible perovskite solar cell device.
The present embodiment is similar to Example 1 for the pattern of hole transmission layer obtained under 90% environment in humidity, and low temperature
The conductivity for handling forward and backward PEDOT:PSS film significantly improves, and roughness is decreased obviously.
In addition, the light of the flexible perovskite solar battery assembled based on PEDOT:PSS hole transmission layer after low-temperature treatment
Photoelectric transformation efficiency has been more than 13.3%, and compared with non-low-temperature treatment, cell photoelectric transfer efficiency improves about 80%.
Embodiment 4:
The preparation method of the flexible perovskite hole transmission layer used for solar batteries of the present embodiment, comprising the following steps:
Firstly, preparing quasi- solidifying state PEDOT:PSS solution；PEDOT:PSS solution and isopropanol are mixed with the volume ratio of 20:1
It closes, then is handled 1 hour under 0 DEG C of low temperature；Clean flexible ITO/PEN conductive substrates are placed in 5 DEG C of low temperature environments simultaneously；
Then PEDOT:PSS solution under conditions of envionmental humidity is 10% by quasi- condensation is added drop-wise to middle flexibility under low temperature environment
In ITO/PET substrate, using spin coating instrument spin coating, revolving speed is 3000 revs/min, and the time is 10 seconds, spin coating process and 1 class of embodiment
Seemingly；Flexible ITO/PET substrate is placed on warm table heating after spin coating, heating temperature is 90 DEG C, is heated 90 minutes；To
PEDOT:PSS film, i.e. hole transmission layer are obtained on a flexible substrate；
Equally, to assemble flexible perovskite solar battery, perovskite light-absorption layer is prepared in hole transport, is made again later
Standby electron transfer layer；Finally, one layer of silver electrode is deposited on the electron transport layer, to obtain flexible perovskite solar cell device
Part.
The pattern of hole transmission layer made from the present embodiment is similar to Example 1；Equally, PEDOT:PSS after low-temperature treatment
The conductivity of film improves to a certain extent, and roughness slightly declines.
In addition, the light of the flexible perovskite solar battery assembled based on PEDOT:PSS hole transmission layer after low-temperature treatment
Photoelectric transformation efficiency has been more than 16.4%, and compared with non-low-temperature treatment, cell photoelectric transfer efficiency improves about 20%.
Embodiment 5:
The preparation method of the flexible perovskite hole transmission layer used for solar batteries of the present embodiment, comprising the following steps:
Firstly, preparing quasi- solidifying state PEDOT:PSS solution；PEDOT:PSS solution and isopropanol are mixed with the volume ratio of 20:1
It closes, then is handled 12 hours under 3 DEG C of low temperature；Clean flexible ITO/PET conductive substrates are placed as 3 DEG C of low temperature environments simultaneously
Under；Then in the PEDOT:PSS solution of quasi- condensation being added drop-wise under low temperature environment under conditions of envionmental humidity is 30%
In flexible ITO/PET substrate, using spin coating instrument spin coating, revolving speed is 4000 revs/min, and the time is 30 seconds, spin coating process and implementation
Example 1 is similar；Flexible ITO/PET substrate is placed on warm table heating after spin coating, heating temperature is 100 DEG C, heats 40 points
Clock；To obtain PEDOT:PSS film, i.e. hole transmission layer on a flexible substrate；
Equally, to assemble flexible perovskite solar battery, perovskite light-absorption layer is prepared in hole transport, is made again later
Standby electron transfer layer；Finally, one layer of silver electrode is deposited on the electron transport layer, to obtain flexible perovskite solar cell device
Part.
The pattern of hole transmission layer made from the present embodiment is similar to Example 1；Compared with non-low-temperature treatment, at low temperature
The conductivity of PEDOT:PSS film increases after reason, and roughness slightly declines.
In addition, the light of the flexible perovskite solar battery assembled based on PEDOT:PSS hole transmission layer after low-temperature treatment
Photoelectric transformation efficiency has been more than 15.5%, and compared with non-low-temperature treatment, cell photoelectric transfer efficiency improves about 35%.
Embodiment 6:
The present embodiment and embodiment one the difference is that:
The volume ratio of PEDOT:PSS solution and isopropanol can be with are as follows: 25:1,30:1 etc.；
It can also be substituted using DMSO or DMF；
Other steps and flexible perovskite solar battery obtained can be with reference implementation examples 1.
The above is only that the preferred embodiment of the present invention and principle are described in detail, to the common skill of this field
For art personnel, the thought provided according to the present invention will change in specific embodiment, and these changes should also regard
For protection scope of the present invention.
Claims (9)
1. a kind of preparation method of flexibility perovskite hole transmission layer used for solar batteries, which comprises the following steps:
(1) PEDOT:PSS solution is mixed with organic cosolvent, the first preset time is handled under 0~10 DEG C of cryogenic conditions,
Obtain spin coating liquid；Also flexible conducting substrate is placed in spin coating instrument and carries out low-temperature treatment, the temperature of the low-temperature treatment is -5~5
℃；
(2) spin coating drop is added to and carries out spin coating on flexible conducting substrate, the compliant conductive of PEDOT:PSS will be loaded after spin coating
Substrate taking-up, which is placed on warm table, to be thermally dried, and flexibility perovskite hole transmission layer used for solar batteries is made.
2. preparation method according to claim 1, which is characterized in that the PEDOT:PSS solution and organic cosolvent
Volume ratio is (20~30): 1.
3. preparation method according to claim 1 or 2, which is characterized in that the organic cosolvent be isopropanol, DMSO or
DMF。
4. preparation method according to claim 1, which is characterized in that first preset time is 1~20 hour.
5. preparation method according to claim 1, which is characterized in that the condition of the spin coating include: revolving speed be 3000~
6000 revs/min, the time is 10~60 seconds, relative humidity 10~90%.
6. preparation method according to claim 5, which is characterized in that the relative humidity is 50%.
7. preparation method according to claim 1, which is characterized in that the condition of the heat drying includes: heating temperature
It is 90~150 DEG C, heating time is 10~90 minutes.
8. a kind of flexibility perovskite hole transmission layer used for solar batteries, which is characterized in that by any one of such as claim 1-7 institute
The preparation method stated is made.
9. the application of flexibility perovskite as claimed in claim 8 hole transmission layer used for solar batteries, which is characterized in that described
Hole transmission layer and the flexible perovskite solar battery of the compound composition of calcium titanium ore bed, electron transfer layer, metal electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002815A (en) * | 2020-07-30 | 2020-11-27 | 隆基绿能科技股份有限公司 | Production method of perovskite thin film and preparation method of perovskite solar cell |
| CN113130763A (en) * | 2021-03-23 | 2021-07-16 | 华南理工大学 | Inverted organic solar cell with double hole transport layers deposited based on solution method and preparation method thereof |
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| US9793056B1 (en) * | 2016-08-10 | 2017-10-17 | The United States Of America As Represented By The Secretary Of The Air Force | Method for producing high quality, ultra-thin organic-inorganic hybrid perovskite |
| CN107275494A (en) * | 2017-06-28 | 2017-10-20 | 南方科技大学 | Blade coating preparation method of flexible perovskite solar cell |
| CN109166971A (en) * | 2018-08-29 | 2019-01-08 | 浙江理工大学 | Enhance the perovskite solar cell preparation method of moisture resistance stability and photoelectric properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9793056B1 (en) * | 2016-08-10 | 2017-10-17 | The United States Of America As Represented By The Secretary Of The Air Force | Method for producing high quality, ultra-thin organic-inorganic hybrid perovskite |
| CN107275494A (en) * | 2017-06-28 | 2017-10-20 | 南方科技大学 | Blade coating preparation method of flexible perovskite solar cell |
| CN109166971A (en) * | 2018-08-29 | 2019-01-08 | 浙江理工大学 | Enhance the perovskite solar cell preparation method of moisture resistance stability and photoelectric properties |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112002815A (en) * | 2020-07-30 | 2020-11-27 | 隆基绿能科技股份有限公司 | Production method of perovskite thin film and preparation method of perovskite solar cell |
| CN113130763A (en) * | 2021-03-23 | 2021-07-16 | 华南理工大学 | Inverted organic solar cell with double hole transport layers deposited based on solution method and preparation method thereof |
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