CN105261703A - Perovskite photovoltaic cell taking Cu: CrOx thin film as hole transporting layer and preparation method for perovskite photovoltaic cell - Google Patents
Perovskite photovoltaic cell taking Cu: CrOx thin film as hole transporting layer and preparation method for perovskite photovoltaic cell Download PDFInfo
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Abstract
The invention belongs to the fields of thin film materials and devices, and in particular relates to a perovskite photovoltaic cell taking a Cu: CrOx thin film as a hole transporting layer and a preparation method for the perovskite photovoltaic cell. The perovskite photovoltaic cell comprises a transparent conductive substrate, a hollow transmission layer Cu: CrOx, a perovskite photosensitive active layer, a negative electrode interface layer and a metal electrode bottom up in sequence; the hollow transmission layer Cu: CrOx takes a copper chrome composite target as the target material, and is obtained by deposition through a reaction radio frequency co-sputtering method; the structure of the copper chrome composite target is that one or several of metal copper wire circular rings are directly placed in an effective sputtering region of the chrome target; the metal copper wire circular rings have the same section area; and the section area of each metal copper wire circular ring is 1/40 of the effective sputtering area of the chrome target. The hollow transmission layer Cu: CrOx thin film prepared by the invention is used as the substitute of an organic material PEDOT: PASS; and the preparation method is simple, the process is simplified and the preparation process is low in cost.
Description
Technical field
The invention belongs to thin-film material and devices field, have and relate to one with Cu:CrO
xfilm is as the perovskite photovoltaic cell and preparation method thereof of hole transmission layer.
Background technology
Solar energy cleans the renewable energy resources as one, has caused and has paid close attention to widely.Recent years, the photovoltaic cell of the perovskite structure of metal halide is a dark horse.This class battery has larger carrier mobility, stronger light absorbing ability and larger open circuit voltage.In 2015, the power conversion efficiency (pce) of perovskite structure breaks through 20% (W.S.Yang, J.H.Noh, N.J.Jeon, Y.C.Kim, S.Ryu, J.Seo, S.I.Seok, High-performancephotovoltaicperovskitelayersfabricatedth roughintramolecularexchange, Science2015, 348, 1234-1237), the efficiency of the perovskite structure photovoltaic cell of planar structure is also up to 18.1% (JinHyuckHeo, HyeJiHan, DasomKim, TaeKyuAhn, SangHyukIm, 18.1%hysteresis-lessinvertedCH3NH3PbI3planarperovskitehy bridsolarcells, EnergyEnviron.Sci., 2015, 8, 1602-1608), flexible battery efficiency is also up to 10% (K.Wojciechowski, M.Saliba, T.Leijtens, A.Abate, H.J.Snaith, EnergyEnviron.Sci.2014, 7, 1142.).In addition, raw material sources extensively, cryogenic fluid prepares and stability better makes it have the prospect of widespread commercial.
In the semiconductors, the mobility of the mobility ratio electronics in hole is low.Selecting appropriate material and preparation technology between anode and photosensitive layer, insert hole transmission layer is the key that perovskite photovoltaic cell obtains stability.
The complex manufacturing technology of conventional organic material hole transmission layer spiro-OMeTAD, cost is higher, affects thus be difficult to commercially produce by water oxygen.Select wide material sources, cost lower and competitive organic substance material PEDOT:PSS (Jengetal, AdvancedMaterials2013,25,3727.) as the replacer of spiro-OMeTAD, but due in atmospheric environment, PEDOT:PSS affects by water oxygen and the person's character of acidity, have impact on the performance of respective battery.Inorganic material CuI (Christiansetal, J.Am.Chem.Soc., 2014,136,758.) less stable, issues solution estranged in the effect of illumination, is difficult to select the choice into appropriate.CuSCN (
etal, NatureCommunications5,2015,3834) there is sterilization (anticorrosion) and insecticidal activity, water is harmful to a little, replacer that neither be suitable.
Inorganic oxide have more stable mechanical performance, good electrical property, lower cost, transparent at visible light part, have good thermal stability and carrier mobility ability, in nanometer to micron size range, be easier to the advantages such as control, cause the research interest of researcher.At present by NiO (Jenetal, AdvancedMaterials, 2015,27,695-701), the Cu of NiO (JengetalAdv.Mater.2014,26,4107 – 4113), Cu doping
2o and CuO (C.Zuo, L.Ding, Small, 2015, DOI:10.1002/smll.201501330) substitutes the hole transmission layer of organic substance PEDOT:PSS as battery.CrO prepared by magnetron sputtering method
xfilm is the complex (Ingleetal, J.Appl.Phys.2001,89:4631-4635.) of a multivalent state, and have good stability, bandwidth is about 3.7eV, but the ability of collecting hole is poor.Under certain temperature and oxygen press strip part, cuprous oxide quite stable, 2.1-2.3eV bandwidth and CH
3nH
3pbI
3can better mate by band, p-type hole mobility is up to 100cm
2/ V
s.Utilize these advantages of cuprous oxide, to CrO
xfilm adulterates, to improve its hole conduction ability thus to be conducive to improving the efficiency of battery.At present, by this Cu:CrO
xthe hole transmission layer being applied to perovskite battery have not been reported.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is to provide a kind of with Cu:CrO
xfilm is as the perovskite photovoltaic cell and preparation method thereof of hole transmission layer.
For achieving the above object, the technical solution used in the present invention is:
A kind of with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, comprises transparent conductive substrate, hole transmission layer Cu:CrO from down to up successively
x, perovskite photosensitive activity layer, cathode interface layer and metal electrode.
In such scheme, described hole transmission layer Cu:CrO
xbe using copper chromium composite target as target, obtained by radio frequency cosputtering method deposition.
In such scheme, the structure of described copper chromium composite target is: with the chromium target center of circle for the center of circle, directly places the different metal copper wire annulus of 1 metal copper wire annulus, 2 diameters or the different metal copper wire annulus of 3 diameters in effective sputtering zone of chromium target.
In such scheme, the sectional area of each metal copper wire annulus is identical, and concrete operations are: the annulus becoming diameter a little bit smaller with the metallic copper filament winding of thick point, the annulus becoming diameter larger with the metallic copper filament winding of choice refreshments.
In such scheme, the sectional area of each metal copper wire annulus is that chromium target effectively sputters 1/40 of area.
In such scheme, the technological parameter of described radio frequency cosputtering method is: background vacuum 1 × 10
-4~ 6 × 10
-3pa; With high-purity Ar and O
2gas respectively as sputtering and reacting gas, O in sputter procedure
2content be 20 ~ 80%, sputtering pressure is 1.0Pa; Sputtering power is 80 ~ 120W; During sputtering, underlayer temperature is 30 ~ 400 DEG C; Sputtering time is 1 ~ 5 minute.
In such scheme, described transparent conductive substrate is ITO electro-conductive glass, FTO electro-conductive glass or be coated with the flexible transparent plastic of ITO.
In such scheme, described perovskite organic photosensitive layer is CH
3nH
3pbI
3; Described cathode interface layer is PCBM.
In such scheme, described metal electrode is Al electrode, Au electrode or Ag electrode.
Above-mentioned with Cu:CrO
xfilm, as the preparation method of the perovskite photovoltaic cell of hole transmission layer, comprises the steps;
(1) clean transparent conductive substrate and dry;
(2) radio frequency cosputtering method is adopted to be deposited on deposition of hole transport layer Cu:CrO in transparent conductive substrate
xfilm;
(3) on hole transmission layer, prepare perovskite photosensitive activity layer;
(4) on perovskite photosensitive activity layer, the method for spin coating is adopted to prepare PCBM cathode interface layer;
(5) last at perovskite photosensitive activity layer surface evaporation metal electrode.
Beneficial effect of the present invention is as follows: the hole transmission layer Cu:CrO prepared by the present invention
xfilm has higher carrier mobility, and its energy level better mates with perovskite photosensitive activity layer energy level, can improve its hole collection ability, Cu:CrO
xfilm is as the replacer of organic material PEDOT:PSS, and in preparation process, method is simple, affects less by O2 to Ar ratio; This invention simplifies technique, reduce preparation technology's cost.
Accompanying drawing explanation
Fig. 1 is the structural representation of chromium-copper composite target described in embodiment 3; 1 is chromium target, and 2 is copper wire, and 3 for effectively to sputter area.
Fig. 2 is Cu:CrO
xfilm is as the perovskite photovoltaic cell structure schematic diagram of hole transmission layer; 4 is transparent conductive substrate, and 5 is Cu:CrO
xfilm, 6 is perovskite CH
3nH
3pbI
3photosensitive layer, 7 is PCBM cathode interface layer, and 8 is metal electrode.
Fig. 3 be embodiment 1-4 prepare with Cu:CrO
xfilm is as the J-V curve of the perovskite photovoltaic cell of hole transmission layer.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In following examples, with Cu:CrO
xfilm, as the preparation method of the perovskite photovoltaic cell of hole transmission layer, comprises the steps:
(1) preparation of target: be that to cut into thickness be 2 millimeters of circular target to 99.99% crome metal block by purity; Be the annulus circle that the metal copper wire of 99.9999% 3 kind of different thicknesses is prepared into three different-diameters by purity: the annulus becoming diameter a little bit smaller with the metallic copper filament winding of thick point, the annulus becoming diameter larger with the metallic copper filament winding of choice refreshments; The cross section metal of three metal copper wire annulus amasss identical, and the cross section metal of each metal copper wire annulus is that chromium target effectively sputters 1/40 of area.
(2) transparent conductive substrate process: the transparent conductive substrate adopted in test is ITO Conducting Glass, FTO Conducting Glass, be coated with flexible transparent plastic (as the polyester resin) substrate of ITO, be commercially available prod or known technology, should first clean transparent conductive substrate before the test: first transparent conductive substrate is cut into suitable shape size, cleaned up with cleaning agent, then tap water, deionized water rinsing, then place it in ultrasonic cleaner and use deionized water successively, ethanol, the each ultrasonic cleaning of acetone 20 minutes, finally use deionized water rinsing, dry up with the high pure nitrogen of drying and dry the transparent conductive substrate that can obtain clean surface.
(3) in transparent conductive substrate, Cu:CrO is deposited
xthe depositing operation of film
A. sputtering target, copper wire ring, substrate are put into the relevant position of settling chamber, adjustment sample rack position, makes it to aim at target surface, and keeps suitable distance.
B. vacuum system is vacuumized: first open cooling water, open mechanical pump, take out low vacuum, after system vacuum is lower than 10Pa, open molecular pump pumping high vacuum, until system vacuum is less than 6 × 10
-3pa.
C. in settling chamber, pass into appropriate high purity oxygen gas and argon gas, make the deposition pressure that oxygen and ar pressure reach required.
D. general radio frequency planar magnetic control sputtering process deposits is adopted: high-purity Ar and O
2gas is respectively as sputtering and reacting gas, and in whole process, oxygen content is in 20% ~ 80% change, and during sputtering, contrast temperature is 30 ~ 400 DEG C of changes, sputtering pressure 1.0Pa, sputtering power 80 ~ 120W, controls film thickness by sedimentation time, and sputtering time is 1 ~ 5 minute.
E., after thin film deposition completes, sample is taken out in shutdown.
(4) solar cell preparation
A.CH
3nH
3the preparation of I: by hydriodic acid aqueous solution (57wt%, AlfaAesar) dense for 15.0mL and 13.5mL methylamine (CH
3nH
2) (40wt%inaqueoussolution, AlfaAesar) react, at 0 DEG C, stir 2 hours in nitrogen atmosphere; Then utilize rotary evaporator to remove desolventizing, obtain ammonium methyl crystalline white powder CH
3nH
3i; Finally, recycling ether is after (AlfaAesar) wash three times, at vacuumize one night, stand-by.
B. one-step method is adopted to prepare perovskite photosensitive activity layer: the CH synthesized by 0.395g
3nH
3i and 1.15gPbI
2(Aldrich) mixed dissolution is in 2mL dimethyl formamide (DMF, AlfaAesar), and stirs 12 hours at 60 DEG C; In the gas tank of inert gas shielding, by the solution for preparing in the mode of spin coating, by 2,000 rpm, the parameter of 30s prepares CH at CrOx/ substrate
3nH
3pbI
3film, then anneals 15 minutes at 100 DEG C; Or
Two-step method is adopted to prepare perovskite photosensitive activity layer: by PbI
2powder is dissolved in dimethyl formamide with the ratio of 550mg/ml, stirs 12 hours, obtain PbI at 70 DEG C
2solution for later use; By the CH of synthesis
3nH
3i white powder is dissolved in isopropyl alcohol (traditional Chinese medicines) in 10.0mg/ml ratio and obtains CH
3nH
3i solution; In the gas tank of inert gas shielding, by the PbI prepared
2the mode of solution spin coating is depositing CrO
xthe transparent conductive substrate of film prepares PbI
2film, high rotating speed controls at 2000rpm, duration 45s; Then it is annealed 30 minutes at 70 DEG C.The PbI finally will prepared
2/ CrO
x/ transparent conductive substrate is at CH
3nH
3soak 5 minutes in I solution, dry up with nitrogen, and annealing 30 minutes at 70 DEG C in atmosphere, obtain CH
3nH
3pbI
3film.
(5) PCBM of 20mg is dissolved in the chlorobenzene solution of 1ml, with spin-coating method at photosensitive layer CH
3nH
3pbI
3pCBM cathode interface layer prepared by film;
(6) at photosensitive layer CH
3nH
3pbI
3evaporated metal electrode on film surface.
The present invention utilizes Keithley2400 tester to Cu:CrO
xfilm carries out the test of J-V curve as the perovskite photovoltaic cell of hole transmission layer.
Embodiment 1
A kind of with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is prepared by the following method:
(1) FTO (SnO of doped with fluorine is cleaned
2) electro-conductive glass sheet: first electro-conductive glass is put into the solution filling cleaning agent (as vertical person who is not a member of any political party's liquid detergent) and soak 10 minutes, after then repeatedly cleaning, clear water rinses; Then polishing is carried out with polishing powder; Then put into the vessel that deionized water, acetone and alcohol are housed respectively and distinguish ultrasonic 20 minutes; Finally put in after de-ionised water twice, dry up by nitrogen gun and put into 80 DEG C, baking oven and dry to eliminate stress.
(2) on FTO substrate, Cu:CrO is prepared
xfilm: chromium target, a metal copper wire annulus and FTO substrate are loaded in magnetron sputtering apparatus, wherein metal copper wire annulus is placed directly on chromium target, sputters with radio-frequency power supply; Condition of work is: base vacuum: 1 × 10
-4pa; O
2/ (Ar+O
2)=40%, underlayer temperature: 200 DEG C, sputtering pressure: 1.0Pa, sputtering power at 120W, sputtering time 1min.
(3) one-step method is adopted to prepare perovskite photosensitive activity layer: the CH synthesized by 0.395g
3nH
3i and 1.15gPbI
2(Aldrich) mixed dissolution is in 2mL dimethyl formamide (DMF, AlfaAesar), and stirs 12 hours at 60 DEG C; In the gas tank of inert gas shielding, by the solution for preparing in the mode of spin coating, by 2,000 rpm, the parameter of 60s prepares CH at CrOx/FTO substrate
3nH
3pbI
3film, then anneals 15 minutes at 100 DEG C;
(4) preparation of cathode interface layer PCBM: with the method for spin coating by 2,000 rpm, the parameter of 60s is at photosensitive layer CH
3nH
3pbI
3pCBM cathode interface layer prepared by film.
(5) preparation of electrode: be about the thick argent electrode of 150nm in the surface evaporation of PCBM cathode interface layer.
Utilize Keithley2400 tester to carry out the test of J-V curve to battery prepared by the present embodiment, test result is shown in Fig. 3, the performance specification of battery: open circuit voltage is: 0.85V; The short circuit current of battery is: 12.22mA/cm
2, fill factor, curve factor is: 56.3%, and energy conversion efficiency is: 5.87%.
Embodiment 2
A kind of with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is prepared by the following method:
(1) ito glass is cleaned: with embodiment 1;
(2) on ITO substrate, Cu:CrO is prepared
xfilm: chromium target, two metal copper wire annulus and ITO substrate are loaded in magnetron sputtering apparatus, wherein metal copper wire annulus is placed directly on chromium target, sputters with radio-frequency power supply, and condition of work is: base vacuum: 6 × 10
-3pa; O
2/ (Ar+O
2)=20%, underlayer temperature: 200 DEG C, sputtering pressure: 1.0Pa, sputtering power at 100W, sputtering time 2min.
(3) two-step method is adopted to prepare perovskite photosensitive activity layer: by PbI
2powder is dissolved in dimethyl formamide with the ratio of 550mg/ml, stirs 12 hours, obtain PbI at 70 DEG C
2solution for later use; By the CH of synthesis
3nH
3i white powder is dissolved in isopropyl alcohol (traditional Chinese medicines) in 10.0mg/ml ratio and obtains CH
3nH
3i solution; In the gas tank of inert gas shielding, by the PbI prepared
2the mode of solution spin coating is depositing CrO
xpbI prepared by the ITO electro-conductive glass of film
2film, high rotating speed controls at 2000rpm, duration 45s; Then it is annealed 30 minutes at 70 DEG C.The PbI finally will prepared
2/ CrO
x/ ITO electro-conductive glass is at CH
3nH
3soak 5 minutes in I solution, dry up with nitrogen, and annealing 30 minutes at 70 DEG C in atmosphere, obtain CH
3nH
3pbI
3film.
(4) preparation of cathode interface layer PCBM: with the method for spin coating by 5,000 rpm, the parameter of 60s is at photosensitive layer CH
3nH
3pbI
3film preparation PCBM cathode interface layer.
(5) preparation of electrode: be about the thick metal aluminium electrode of 150nm in the surface evaporation of PCBM cathode interface layer.
Utilize Keithley2400 tester to carry out the test of J-V curve to battery prepared by the present embodiment, test result is shown in Fig. 3, the performance specification of battery: 0.97V, and the short circuit current of battery is: 12.48mA/cm
2, fill factor, curve factor is: 65.0%, and energy conversion efficiency is: 7.84%.
Embodiment 3
A kind of with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is prepared by the following method:
(1) cleaning of the flexible transparent plastic substrate of ITO is coated with: with embodiment 1.
(2) on the flexible transparent plastic substrate being coated with ITO, Cu:CrO is prepared
xfilm: chromium target, three metal copper wire annulus and the flexible transparent plastic substrate that is coated with ITO are loaded in magnetron sputtering apparatus, wherein metal copper wire annulus is placed directly on chromium target, sputters with radio-frequency power supply, and condition of work is: base vacuum: 6 × 10
-3pa; O
2/ (Ar+O
2)=40%, underlayer temperature: 30 DEG C, sputtering pressure: 1.0Pa, sputtering power at 80W, sputtering time 5min.
(3) two-step method is adopted to prepare perovskite photosensitive activity layer: with embodiment 2.
(4) preparation of cathode interface layer PCBM: with embodiment 1.
(5) preparation of electrode: be about the thick gold electrode of 200nm in the surface evaporation of PCBM cathode interface layer.
Utilize Keithley2400 tester to carry out the test of J-V curve to battery prepared by the present embodiment, test result is shown in Fig. 3, and the performance parameter of battery illustrates: opens voltage is: 0.91V, and the short circuit current in pond is: 11.79mA/cm
2, fill factor, curve factor is: 60.5%, and energy conversion efficiency is: 6.49%.
Embodiment 4
A kind of with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is prepared by the following method:
(1) FTO glass is cleaned: with embodiment 1.
(2) in FTO glass substrate, Cu:CrO is prepared
xfilm: chromium target, a metal copper wire annulus and FTO glass substrate are loaded in magnetron sputtering apparatus, wherein metal copper wire annulus is placed directly on chromium target, sputters with radio-frequency power supply.Condition of work is: base vacuum: 1 × 10
-4pa; O
2/ (Ar+O
2)=80%, underlayer temperature: 400 DEG C, sputtering pressure: 1.0Pa, sputtering power at 100W, sputtering time 3min.
(3) two-step method is adopted to prepare perovskite photosensitive activity layer: with embodiment 2.
(4) preparation of cathode interface layer PCBM: with embodiment 1.
(5) preparation of electrode: with embodiment 1.
Utilize Keithley2400 tester to carry out the test of J-V curve to battery prepared by the present embodiment, test result is shown in Fig. 3, and the performance parameter of the battery obtained illustrates: open circuit voltage is 0.90V, and short-circuit current density is 10.8mA/cm
2, fill factor, curve factor is 35.8%, and photoelectric conversion efficiency is 3.48%.
Obviously, above-described embodiment is only for the example done clearly is described, and the restriction not to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all execution modes.And therefore amplified apparent change or variation are still within the protection range of the invention.
Claims (10)
1. one kind with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, comprises transparent conductive substrate, hole transmission layer Cu:CrO from down to up successively
x, perovskite photosensitive activity layer, cathode interface layer and metal electrode.
2. according to claim 1 with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, described hole transmission layer Cu:CrO
xbe using copper chromium composite target as target, obtained by radio frequency cosputtering method deposition.
3. according to claim 2 with Cu:CrO
xfilm is as the perovskite photovoltaic cell of hole transmission layer, it is characterized in that, the structure of described copper chromium composite target is: with the chromium target center of circle for the center of circle, directly places the different metal copper wire annulus of 1 metal copper wire annulus, 2 diameters or the different metal copper wire annulus of 3 diameters in effective sputtering zone of chromium target.
4. according to claim 3 with Cu:CrO
xfilm is as the perovskite photovoltaic cell of hole transmission layer, it is characterized in that, the sectional area of each metal copper wire annulus is identical, and concrete operations are: the annulus becoming diameter a little bit smaller with the metallic copper filament winding of thick point, the annulus becoming diameter larger with the metallic copper filament winding of choice refreshments.
5. according to claim 3 with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, the sectional area of each metal copper wire annulus is that chromium target effectively sputters 1/40 of area.
6. according to claim 1 with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, the technological parameter of described radio frequency cosputtering method is: background vacuum 1 × 10
-4~ 6 × 10
-3pa; With high-purity Ar and O
2gas respectively as sputtering and reacting gas, O in sputter procedure
2content be 20 ~ 80%, sputtering pressure is 1.0Pa; Sputtering power is 80 ~ 120W; During sputtering, the temperature of transparent conductive substrate is 30 ~ 400 DEG C; Sputtering time is 1 ~ 5 minute.
7. according to claim 1 with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, described transparent conductive substrate is ITO electro-conductive glass, FTO electro-conductive glass or be coated with the flexible transparent plastic of ITO.
8. according to claim 1 with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, described perovskite photosensitive activity layer is CH
3nH
3pbI
3; Described cathode interface layer is PCBM.
9. according to claim 1 with Cu:CrO
xfilm, as the perovskite photovoltaic cell of hole transmission layer, is characterized in that, described metal electrode is Al electrode, Au electrode or Ag electrode.
10. claim 1 ~ 9 is arbitrary described with Cu:CrO
xfilm, as the preparation method of the perovskite photovoltaic cell of hole transmission layer, is characterized in that, comprises the steps;
(1) clean transparent conductive substrate and dry;
(2) radio frequency cosputtering method is adopted to be deposited on deposition of hole transport layer Cu:CrO in transparent conductive substrate
xfilm;
(3) on hole transmission layer, adopt one-step method or two-step method to prepare perovskite photosensitive activity layer;
(4) on perovskite photosensitive activity layer, spin-coating method is adopted to prepare PCBM cathode interface layer;
(5) at PCBM cathode interface layer surface evaporation metal electrode.
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|---|---|---|---|
| CN201510796333.4A CN105261703B (en) | 2015-11-18 | 2015-11-18 | One kind is with Cu:CrOxThe perovskite photovoltaic cell of film as hole transmission layer and preparation method thereof |
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|---|---|---|---|
| CN201510796333.4A CN105261703B (en) | 2015-11-18 | 2015-11-18 | One kind is with Cu:CrOxThe perovskite photovoltaic cell of film as hole transmission layer and preparation method thereof |
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| CN105261703B CN105261703B (en) | 2018-05-01 |
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| CN201510796333.4A Expired - Fee Related CN105261703B (en) | 2015-11-18 | 2015-11-18 | One kind is with Cu:CrOxThe perovskite photovoltaic cell of film as hole transmission layer and preparation method thereof |
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| CN106252517A (en) * | 2016-10-10 | 2016-12-21 | 武汉工程大学 | A kind of with Cuycrzo2thin film is perovskite photovoltaic cell of hole transmission layer and preparation method thereof |
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| CN106876596A (en) * | 2017-02-21 | 2017-06-20 | 华侨大学 | With Cr2O3It is the preparation method of the perovskite solar cell of electron-transporting material |
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