CN106328821B - A kind of method for preparing perovskite solar cell hole transmission layer cobalt oxide films - Google Patents
A kind of method for preparing perovskite solar cell hole transmission layer cobalt oxide films Download PDFInfo
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- CN106328821B CN106328821B CN201610877389.7A CN201610877389A CN106328821B CN 106328821 B CN106328821 B CN 106328821B CN 201610877389 A CN201610877389 A CN 201610877389A CN 106328821 B CN106328821 B CN 106328821B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/085—Oxides of iron group metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
The present invention relates to a kind of method for preparing perovskite solar cell hole transmission layer cobalt oxide films, including：Using metallic cobalt as the first target, using argon gas and oxygen as sputter gas, cobalt oxide films are deposited in substrate surface using direct magnetic control co-sputtering method；Wherein, the power of the dc source put on first target is 100~700 W or power density is 1.3~8.9 W/cm2；The total pressure for controlling sputter gas is 0.5~2.5 Pa, and partial pressure of oxygen is less than 50%；Sedimentation time is 1~5 minute.The present invention prepares cobalt oxide films using direct magnetic control co-sputtering method, and by controlling the sputtering power or/and atmosphere pressures of the first target, the energy of deposited particles in sputter chamber is improved, it is hereby achieved that the cobalt oxide films of the ratio with different divalent cobalt ions and trivalent cobalt ions.
Description
Technical field
The invention belongs to field of inorganic nano material, and in particular to one kind prepares perovskite solar cell hole transmission layer
With cobalt oxide films and pass through the method for ion doping optimization.
Background technology
In recent years, gradually aggravate in energy crisis, under the background that environmental gradually deepens, global photoelectricity research neck
Domain achieves great progress, turns into this century most one of study hotspot of prospect and strategic importance.In this area, due to
Cost is low, technique is simple and excellent performance, and perovskite solar cell becomes the study hotspot of field of photoelectric devices.The electricity
The sun light conversion efficiency that pond proposes for 2009 first is only 4%, and by the development of 7 years, nowadays authentication efficiency was up to
22%, the electricity conversion current more than non-crystal silicon solar cell and copper indium gallium selenium solar cell, there is the monocrystalline that matches in excellence or beauty
The potentiality of silicon and multi-junction gallium arsenide battery.Therefore, the research for perovskite battery is actively developed, optimizes battery structure and composition
Material, and innovation and development sustainable to national economy from now on have great meaning.Realize that battery possesses the base of high conversion efficiency
This approach is exactly to improve the extraction of photo-generated carrier, the ability of separation and transport.
Perovskite solar cell includes 5 layer materials, and this several layer material has different performances respectively.It is transparent lead first
Electrode, conventional is FTO (mixing F tin ash) or ITO (tin indium oxide) electro-conductive glass；Electron transfer layer is followed by, is used
In transporting light induced electron in time and stopping photohole, suppress the compound of light induced electron and photohole；It is that perovskite is inhaled again
Receive material, mainly Ca-Ti ore type Organic leadP halide (ABX3:A=CH3NH3, B=Pb, X=Cl, I, Br)；It is hole again
Transport layer, for transporting photohole in time and stopping light induced electron, suppress the compound of light induced electron and photohole；It is finally
Back electrode, conventional is gold, silver and copper.Therefore, suitable hole transmission layer is that high performance calcium titanium ore solar energy is indispensable
A part.
Preferable hole transmission layer has outstanding cavity transmission ability and electron-blocking capability, has in visible-range
Standby high transmittance, relatively low interface resistance, and the energy level of matching perovskite absorbed layer valence band location.Up to the present, mainly
It is organic matter such as PEDOT:Hole transmission layers of the PSS and Spiro-MATeD as perovskite battery, preparation method are also only capable of selecting
Spin-coating method.The unstability of organic matter determines corresponding battery life, and spin-coating method prepares film and limited by size and uniformity
System.
The content of the invention
The present invention asks for what prior art hole-transporting layer secular instability and preparation technology were subject to many limitations
Topic is, and it is an object of the present invention to provide a kind of hole transmission layer cobalt oxide films preparation method.
On the one hand, the invention provides a kind of preparation of perovskite solar cell hole transmission layer cobalt oxide films
Method, including：Using metallic cobalt as the first target, using argon gas and oxygen as sputter gas, using direct magnetic control co-sputtering method
Cobalt oxide films are deposited in substrate surface；Wherein, the power of the dc source put on first target be 100~
700W or power density are 1.3~8.9W/cm2；The total pressure for controlling sputter gas is 0.5~2.5Pa, partial pressure of oxygen 50%
Below；Sedimentation time is 1~5 minute.
The present invention prepares cobalt oxide films using direct magnetic control co-sputtering method, and by controlling the sputtering work(of the first target
Rate or/and atmosphere pressures, improve sputter chamber in deposited particles energy, it is hereby achieved that with different divalent cobalt ions with
The cobalt oxide films of the ratio of trivalent cobalt ions.In addition, the present invention can also can obtain difference by controlling sputtering time
The cobalt/cobalt oxide nano thin-film of thickness.Cobalt oxide films prepared by the present invention have outstanding hole transport performance, are used
Make in perovskite solar cell hole transmission layer, can be matched with perovskite absorbed layer valence band.
It is preferred that also contain doped metal ion in the cobalt oxide films, doping metals source be copper, nickel, magnesium, aluminium,
At least one of zinc and titanium；
Preparation method includes：Mixed using metallic cobalt as the first target, with least one of copper, nickel, magnesium, aluminium, zinc and titanium
Miscellaneous metal as the second target, using argon gas and oxygen as sputter gas, sunk using direct magnetic control co-sputtering method in substrate surface
Product cobalt oxide films；Wherein, the power of the dc source put on first target is that 100~700W or power are close
Spend for 1.3~8.9W/cm2；The power of the dc source put on second target is 5~50W or power density is
0.065~0.65W/cm2；The total pressure for controlling sputter gas is 0.5~2.5Pa, and partial pressure of oxygen is less than 50%；Sedimentation time is
1~5 minute.The present invention can control doped metal ion (example by the sputtering power or/and atmosphere pressures for controlling the second target
Such as copper ion) valence state.Therefore, by controlling cosputtering power and/or atmosphere pressures, deposited particles in sputter chamber are improved
Energy, it is hereby achieved that the cobalt oxide films of different composition, including the ratio of divalent cobalt ion and trivalent cobalt ions and mix
The valence state of heteroion, the ratio of doping can be adjusted by the power of condition doping metals target.
It is preferred that second target is at least one of copper, nickel, magnesium and aluminium, preferably copper.In the present invention, pass through
The doped metal ion in cobalt oxide films, the valence band location of cobalt/cobalt oxide can be adjusted and improve the hole transport energy of film
Power.When adulterating copper ion, the position of energy band of oxidation cobalt thin film can be adjusted, is made it possible to the highest of perovskite absorbing material not
It is occupied track to match, this is the premise for obtaining excellent properties.
Also, it is preferred that the power of the dc source on second target is 10~30W.
It is preferred that the power of the dc source on first target is 100~500W, preferably 300~500W.
It is preferred that the total pressure for controlling sputter gas is 1~2.5Pa, preferably 2Pa, partial pressure of oxygen 20-40%.
It is preferred that first target or/and the distance of the second target and substrate are 7~20cm；Initial substrate temperature is
Room temperature, base reservoir temperature is below 80 DEG C at the end of deposition；Background vacuum is less than 10-4Pa.In the present invention, the initial temperature of substrate
For room temperature, need not be heated in whole process.
On the other hand, present invention also offers a kind of cobalt oxide films, Co in the cobalt oxide films2+、Co3+With
The mol ratio of doped metal ion is (50~100):(50~100):(0~5).
It is preferred that the cobalt oxide films thickness is 5~20nm, it is seen that light transmission rate reaches 50~80%.The thickness
Degree can be regulated and controled by controlling sputtering time.
Another further aspect, the invention provides a kind of preparation method of perovskite solar cell, including：Led successively transparent
Cobalt oxide films, perovskite light absorbing layer, electron transfer layer and back electrode are deposited in electric substrate, wherein the cobalt/cobalt oxide
Film is adopted to be made with the aforedescribed process.In one embodiment, the preparation method of perovskite solar cell may include as follows
Step：
(A) cobalt oxide films (hole transport is deposited in the electrically conducting transparent substrate of cleaning using direct current magnetron sputtering process
Layer)；
(B) spin coating or double source coevaporation prepare perovskite light absorbing layer on the cobalt oxide films of gained；
(C) the spin coating electron transfer layer on the perovskite light absorbing layer of gained；
(D) the vacuum evaporation back electrode on the electron transfer layer of gained.
It is preferred that in step (A), the electrically conducting transparent substrate is one kind in FTO glass, AZO glass, IT glass.
It is preferred that in step (B), described perovskite light absorbing layer is Ca-Ti ore type Organic leadP halide (ABX3：A=
CH3NH3, B=Pb, X=Cl, I, Br).
In step (C), described electron transfer layer can be TiO2, ZnO, PEDOT:At least one of PSS.
In step (D), back electrode can be gold, silver, copper etc..
Cobalt oxide films prepared by the present invention have the characteristics of ultra-thin, interface densification, continuous uniform and low roughness.This
The band gap of kind material more matches perovskite absorbed layer, can efficiently separate and transmit photohole, while stops that electronics passes
It is defeated.Compared to traditional inorganic hole-transporting layer, cobalt oxide films proposed by the present invention have higher stability.In addition room temperature
Prepared by magnetron sputtering allows us to prepare large area or the battery based on flexible substrate.
The present invention provides room temperature DC sputturing method and prepares the method for mixing copper cobalt oxide films, and the film is applied to perovskite
The mesoporous layer of solar cell.By controlling cosputtering power and atmosphere pressures, the energy of deposited particles in sputter chamber is improved, from
And the cobalt oxide films of different compositions can be obtained, including the ratio and Doped ions of divalent cobalt ion and trivalent cobalt ions
Valence state.By controlling sputtering time, the cobalt/cobalt oxide nano thin-film of different-thickness can be obtained.
The method of the invention is a kind of simple and fast, while can control film quality, film thickness and property again
Method.Film prepared by this room temperature magnetron sputtering has outstanding photohole separation and efficiency of transmission (transport capacity).It is logical
Appropriate ion doping is crossed, the performance of gained film can be improved further.Therefore, based on cobalt/cobalt oxide hole transmission layer calcium titanium
Ore deposit solar cell has higher photoelectric transformation efficiency, and stability significantly improves.Room temperature sputtering method not only simplifies tradition
Battery preparation technique, it is cost-effective, and the performance based on the hull cell can be improved, it may advantageously facilitate perovskite solar energy
The large-scale production and the marketization of battery.
The method of the invention compared with prior art, has advantages below：
(1) magnetron sputtering method short preparation period, can be unrestricted in substrate dimension and uniformity of film with continuous control；
(2) preparation technology is simple, and stable high, reproducible, market-oriented application prospect is fine；
(3) a kind of inorganic hole-transporting layer is used as, significantly improves stability test.
Brief description of the drawings
Fig. 1 is magnetic control co-sputtering schematic diagram in the present invention；
A is the cobalt oxide films surface of non-gold doping category prepared by embodiment 2 in Fig. 2, and B, C, D are respectively that embodiment 5 is made
SEM figures (B in Fig. 2), section SEM (C in Fig. 2) and the EDS figures (D in Fig. 2) on the standby cobalt oxide films surface for mixing copper；
Fig. 3 is the embodiment of the present invention 2, the different Cu Doped Power film visible light transmissivity of embodiment 4-7 preparations and office
Portion's enlarged drawing (illustration in Fig. 3), wherein the first target as sputter power is 300W, Doped Power is incremented by successively；
Fig. 4 is based upon the solar-electricity of cobalt oxide films prepared by the embodiment of the present invention 2, embodiment 4-7, embodiment 9
Pond performance；
Fig. 5 be the present invention prepare based on cobalt oxide hole transmission layer perovskite solar battery structure schematic diagram；
Fig. 6 is the XPS analysis figure of cobalt oxide films.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The invention provides prepare perovskite solar cell hole transmission layer with cobalt oxide films and mixed by ion
The method of miscellaneous optimization, the film even compact, surface roughness is low, is firmly combined with base material, in visible region transmitance
It is good.With outstanding cavity transmission ability and electron-blocking capability.And the film surface wetability is good, perovskite absorbing material
Contact can be very good in its surface spreading, thus can reduce interface contact resistance accordingly.
Illustrate to following exemplary the preparation method of cobalt oxide films provided by the invention.
Referring to Fig. 1, DC magnetron sputtering system equipment used in deposition can include deposition chambers, Sample Room, two
Target plate, a underboarding, two dc sources and a series of vavuum pump are carried, wherein carrying target plate and underboarding into certain angle
Degree, dc source, which is connected to, to be carried on target plate.Two carry and load pure cobalt target (the first target) and doping metals target (the on target plates respectively
Two targets).
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In deposition chambers below during Pa.
Specific deposition process, high-purity argon gas and oxygen mixed gas are passed through in deposition chambers, used argon gas and
The purity of oxygen can be more than 99.99%.Total pressure and partial pressure of oxygen are controlled respectively in 0.5-2.5Pa and less than 50%.It is wherein total
Pressure is preferably 0.5-2Pa, and partial pressure of oxygen is preferably 20-40%.It is 7-20cm to control the distance of the first target and base material.First primordium
Bottom temperature is room temperature, and extra heating is not needed in whole process.Control partial pressure of oxygen can be by controlling oxygen in the present invention
Realize that the volume ratio of wherein oxygen and argon gas is preferably 1 with the volume ratio of argon gas:1-1:5, more preferably 1:1-1:3, most preferably
For 1:2
It is then turned on dc source, controls the Dc source power of the first target to 100-700W, preferably 100~
500W, more preferably 300~500W, most preferably 300W.Now, the Dc source power of the second target is 0 (i.e. the second target
Without sputtering).It can be 1-5 minutes to control sedimentation time.After deposition terminates, substrate is waited to be dropped due to temperature caused by particle bombardment
Room temperature is returned to, takes out base material (electrically conducting transparent substrate, substrate or substrate etc. can be claimed).Thus be made be deposited on base material (such as FTO lining
Bottom) on the cobalt oxide films undoped with metal.
Or dc source is opened, the power for controlling the first target dc source is 100-700W, preferably 100~
500W, more preferably 300~500W, most preferably 300W, sputter pure cobalt target.Control the second target (for example, copper target, nickel target,
Magnesium target and aluminium target etc.) power of dc source is that 5-50W (being preferably 10-30W, more preferably 15W) or power density can
For 0.065~0.65W/cm2, while sputter the second target.Control sedimentation time 1-5 minutes.After deposition terminates, wait substrate (can
Claim base material or substrate etc.) because temperature caused by particle bombardment rolls back room temperature, take out base material.Thus it is made and is deposited on substrate
The cobalt oxide films of doping metals on (for example, FTO substrates).By the sputtering work(for adjusting the first target and the second target
Rate, it is possible to achieve the ratio between divalent cobalt ion and trivalent cobalt ions and copper ion.By shared by control pressure and oxygen
Ratio, the valence state of copper ion can be adjusted.
As an example, prepared using direct magnetic control co-sputtering method, wherein target is pure cobalt target and copper target, sputter gas
For argon gas and oxygen, total pressure is 0.5~2.5Pa, and partial pressure of oxygen is 0~50%.The distance of target and substrate is 7~20cm.Just
Beginning base reservoir temperature is room temperature, and the power of the dc source put on the cobalt target is 300W.Put on straight in the copper target
The power for flowing power supply is 15W.Base reservoir temperature is below 80 DEG C at the end of deposition.Wherein sedimentation time is 1~5 minute.
Pre-sputtering can be first carried out in the above method before cobalt oxide films are deposited, the wherein condition of pre-sputtering can be：Work(
Rate can be 100-300W, and the time can be 5-30 minutes, and atmosphere is pure argon, and gas pressure can be 0.5-1.5Pa.
It is evaporated in vacuo in this method and magnetron sputtering initial background vacuum is below 10-4Pa。
Present invention also offers a kind of perovskite solar cell, including：Successively cobalt oxide is deposited in electrically conducting transparent substrate
Compound film, perovskite light absorbing layer, electron transfer layer and back electrode, wherein the cobalt oxide films use above-mentioned side
Method is made.
Referring to Fig. 5, illustrate to the example below the preparation method of perovskite solar cell provided by the invention.
Cobalt oxide films (example is deposited in the electrically conducting transparent substrate (for example, FTO) of cleaning using direct current magnetron sputtering process
Such as, Cu：CoOx)。
On gained cobalt oxide films spin coating or double source coevaporation prepare perovskite light absorbing layer (for example,
CH3NH3PbI3)。
Spin coating electron transfer layer (for example, PCBM, a kind of fullerene derivate) on the perovskite light absorbing layer of gained.
Vacuum evaporation back electrode (for example, Ag) on the electron transfer layer of gained.
Cobalt oxide films prepared by the present invention have excellent hole transport performance and long-time stability.In an example
In, adulterated by cuprous ion, the valence band location of cobalt/cobalt oxide can be adjusted and improve film cavity transmission ability.Therefore it is based on
Copper-cladding Aluminum Bar cobalt/cobalt oxide hole transmission layer perovskite solar cell prepared by cosputtering method has outstanding photoelectric transformation efficiency.
Based on above-mentioned excellent performance, prepared by the present invention mixes the sky for being applied to perovskite solar cell in metal cobalt oxide films
Cave transport layer, can be efficiently separated and transporting holes, while have long-time stability.Analyzed by AFM, it is known that mixing copper
Cobalt/cobalt oxide has the roughness of very little.By XPS analysis, it can accurately learn and know that composition is divalent cobalt ion in film,
Trivalent cobalt ions, doped metal ion (such as cuprous ion) and divalence oxonium ion.By field emission scanning electron microscope and
Transmission electron microscope can study the pattern and composition of film.Tested by ultraviolet-visible spectrophotometer, it is known that institute
Obtain film transmitance in visible-range and reach 80%., can be with table by steady-state fluorescence spectrometer and transient state XRF
Levy electronics extraction and the separative efficiency of different levels of doping film.By IPCE it is recognised that being based on different Doped Power films
The perovskite solar cell of preparation has different light quantum conversion efficiencies.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 500W, and copper target power is
0W), sedimentation time 2min.Understanding after tested, the thickness of obtained cobalt oxide films is 20nm, roughness 5.912,
Transmitance is 72% in visible-range.It is last according to it has been reported that method prepare composition perovskite solar energy again on sample
Other layer materials needed for battery, including prepare perovskite absorbed layer (double source coevaporation PbI2And CH3NH3I), spin coating prepares empty
Cave transport layer (raw material Spiro-OMeTAD, rotating speed 2600r/min) and vacuum evaporation prepare back electrode (raw material Ag,
Evaporation current 125A, evaporation time 15min).Solar battery efficiency is 3.12%.By XPS analysis, it is known that in film
Composition is divalent cobalt ion, trivalent cobalt ions and divalence oxonium ion.
Embodiment 2
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 300W, and copper target power is
0W), sedimentation time 2min.Understanding after tested, the thickness of obtained cobalt oxide films is 14nm, roughness 5.021,
Transmitance is 75% in visible-range.Referring finally to embodiment 1, composition perovskite solar cell institute is prepared again on sample
Other layer materials needed, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and vacuum evaporation prepares back electrode, and
And its photoelectric transformation efficiency is tested, it is as a result 3.68%.By XPS analysis, it is known that composition is divalent cobalt ion in film,
Trivalent cobalt ions and divalence oxonium ion.
Embodiment 3
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 100W, and copper target power is
0W), sedimentation time 2min.Understanding after tested, the thickness of obtained cobalt oxide films is 8nm, roughness 7.013,
Transmitance is 80% in visible-range.Referring finally to embodiment 1, composition perovskite solar cell institute is prepared again on sample
Other layer materials needed, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and vacuum evaporation prepares back electrode, and
And its photoelectric transformation efficiency is tested, it is as a result 2.91%.By XPS analysis, it is known that composition is divalent cobalt ion in film,
Trivalent cobalt ions and divalence oxonium ion.It is can be seen that from embodiment 1-3 by adjusting cobalt target power output, it can be deduced that performance is optimal
When actual conditions, by XPS analysis, we can draw specific Co3+And Co2+Between ratio.As shown in Figure 6, its
In 1. represent Co2O3Middle O content, the content of O in CoO is 2. represented, therefore 1. and 2. occupied area understands O between the two for contrast
Ratio is 3:1, it can be deduced that Co when performance is optimal3+And Co2+Between ratio be 2:1(Co2O3Middle Co and O ratios are 2:3).
Embodiment 4
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 300W, and copper target power is
5W), sedimentation time 2min.Understanding after tested, the thickness of obtained cobalt oxide films is 15nm, roughness 4.991nm,
Transmitance is 74% in visible-range.Referring finally to embodiment 1, composition perovskite solar cell is prepared again on sample
Other required layer materials, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and vacuum evaporation prepares back electrode,
And its photoelectric transformation efficiency is tested, is as a result 6.48%.By XPS analysis, it is known that in film composition be divalence cobalt from
Son, trivalent cobalt ions, cuprous ion and divalence oxonium ion.
Embodiment 5
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opening gate is loaded into vacuum (background vacuum) and reached
In below 10-4Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa, target and substrate to control total pressure
Distance be 8cm, initial chamber temp keeps opening dc source at ambient temperature, and (cobalt target power output is 300W, copper target work(
Rate is 15W), sedimentation time 2min.Understand after tested, the thickness of obtained cobalt oxide films is 15nm, and roughness is
4.990nm, transmitance is 73% in visible-range.Referring finally to embodiment 1, composition perovskite is prepared again on sample too
Other layer materials needed for positive energy battery, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and is evaporated in vacuo and makes
Standby back electrode, and its photoelectric transformation efficiency is tested, it is as a result 9.98%.By XPS analysis, it is known that composition is in film
Divalent cobalt ion, trivalent cobalt ions, cuprous ion and divalence oxonium ion.
Embodiment 6
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 300W, and copper target power is
25W), sedimentation time 2min.Understand after tested, the thickness of obtained cobalt oxide films is 16nm, and roughness is
4.993nm, transmitance is 71% in visible-range.Referring finally to embodiment 1, composition perovskite is prepared again on sample too
Other layer materials needed for positive energy battery, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and is evaporated in vacuo and makes
Standby back electrode, and its photoelectric transformation efficiency is tested, it is as a result 4.91%.By XPS analysis, it is known that composition is in film
Divalent cobalt ion, trivalent cobalt ions, cuprous ion and divalence oxonium ion.
Embodiment 7
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 300W, and copper target power is
50W), sedimentation time 2min.Understand after tested, the thickness of obtained cobalt oxide films is 17nm, and roughness is
4.882nm, transmitance is 70% in visible-range.Referring finally to embodiment 1, composition perovskite is prepared again on sample too
Other layer materials needed for positive energy battery, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and is evaporated in vacuo and makes
Standby back electrode, and its photoelectric transformation efficiency is tested, it is as a result 3.77%.By XPS analysis, it is known that composition is in film
Divalent cobalt ion, trivalent cobalt ions, cuprous ion and divalence oxonium ion.
Fig. 2 is that the cobalt oxide films surface (A in Fig. 2) of non-gold doping category prepared by embodiment 2 is mixed with prepared by embodiment 5
SEM figures, section SEM (C in Fig. 2) and the EDS figures (D in Fig. 2) on the cobalt oxide films surface (B in Fig. 2) of copper.A can from Fig. 2
That knows sull even compact prepared by this experiment is covered in FTO substrate surfaces, and B understands Copper-cladding Aluminum Bar oxygen prepared by this experiment
Compound film even compact is covered in FTO substrate surfaces, and C understands that Copper-cladding Aluminum Bar sull thickness is about 14nm, and D understands copper
Element is doped into film.
Fig. 3 is the embodiment of the present invention 2, the different Cu Doped Power film visible light transmissivity of embodiment 4-7 preparations and office
Portion's enlarged drawing (illustration in Fig. 3), as can be seen from Figure 3 as the lifting of Doped Power, film transmission rate gradually reduce.Fig. 4 is based upon
The solar cell properties of cobalt oxide films prepared by the embodiment of the present invention 2, embodiment 4-7, embodiment 9, rise as can be seen from Figure 4
Just as the increase of doping, perovskite solar cell properties gradually step up.But Doped Power more than 15W when, it is cell performance
Can gradually it be reduced with the raising of Doped Power.According to Fig. 3 it will be seen that with the lifting of Doped Power, film it is saturating
Crossing rate gradually reduces, therefore can prove that this is due to the gold that can prove doping caused by the raising of Doped Power in turn
Category ion is successfully entered in film.
Embodiment 8
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 500W, and nickel target power output is
20W), sedimentation time 2min.Understand after tested, the thickness of obtained cobalt oxide films is 16nm, and roughness is
4.919nm, transmitance is 77% in visible-range.Referring finally to embodiment 1, composition perovskite is prepared again on sample too
Other layer materials needed for positive energy battery, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and is evaporated in vacuo and makes
Standby back electrode, and its photoelectric transformation efficiency is tested, it is as a result 9.36%.By XPS analysis, it is known that composition is in film
Divalent cobalt ion, trivalent cobalt ions, bivalent nickel ion, divalence oxonium ion.
Embodiment 9
Base material (FTO glass) is cleaned by ultrasonic, after being cleaned by ultrasonic base material each 30 minutes with acetone and absolute ethyl alcohol respectively, had
It is fixed on underboarding to sequence, is put into Sample Room, then opens gate and be loaded into vacuum (background vacuum) and reached 10- 4In below Pa deposition chambers.Ratio is passed through as 1:2 oxygen and argon gas, it is 2Pa to control total pressure, target and substrate away from
From for 8cm, initial chamber temp keeps opening dc source at ambient temperature that (cobalt target power output is 300W, and copper target power is
20W), sedimentation time 2min.Understand after tested, the thickness of obtained cobalt oxide films is 16nm, and roughness is
4.902nm, transmitance is 72% in visible-range.Referring finally to embodiment 1, composition perovskite is prepared again on sample too
Other layer materials needed for positive energy battery, including perovskite absorbed layer is prepared, spin coating prepares electron transfer layer and is evaporated in vacuo and makes
Standby back electrode, and its photoelectric transformation efficiency is tested, it is as a result 7.14%.By XPS analysis, it is known that composition is in film
Divalent cobalt ion, trivalent cobalt ions, cuprous ion and divalence oxonium ion.
Industrial applicability：The present invention prepares the cobalt/cobalt oxide that thickness mixes copper for 5-20nm, and film surface even compact,
Roughness is low, it is seen that transmitance is high in optical range.More importantly it is that the film has outstanding hole transport efficiency and electronics
Blocking capability, and long-time stability are good, can effectively improve the opto-electronic conversion based on the thin film perovskites solar cell
Efficiency and stability test.Therefore the present invention has very big application and market-oriented prospect.
Claims (12)
- A kind of 1. preparation method of perovskite solar cell hole transmission layer cobalt oxide films, it is characterised in that including： Using metallic cobalt as the first target, using argon gas and oxygen as sputter gas, using direct magnetic control co-sputtering method in substrate surface Deposit cobalt oxide films；Wherein, the power of the dc source put on first target be 100~700 W or Power density is 1.3~8.9 W/cm2；The total pressure for controlling sputter gas is 0.5~2.5 Pa, and partial pressure of oxygen is less than 50%；It is heavy The product time is 1~5 minute.
- 2. preparation method according to claim 1, it is characterised in that also contain doping metals in the cobalt oxide films Ion, doping metals source are at least one of copper, nickel, magnesium, aluminium, zinc and titanium；Preparation method includes：Make using metallic cobalt as the first target, using doping metals source as the second target, with argon gas and oxygen For sputter gas, cobalt oxide films are deposited in substrate surface using direct magnetic control co-sputtering method；Wherein, described first is put on The power of dc source on target is 100~700 W or power density is 1.3~8.9 W/cm2；Put on described The power of dc source on two targets is 5~50 W or power density is 0.065~0.65 W/cm2；Control sputter gas Total pressure be 0.5~2.5 Pa, partial pressure of oxygen is less than 50%；Sedimentation time is 1~5 minute.
- 3. preparation method according to claim 2, it is characterised in that second target be copper, nickel, magnesium and aluminium in extremely Few one kind.
- 4. the preparation method according to Claims 2 or 3, it is characterised in that the work(of the dc source on second target Rate is 10~30W.
- 5. preparation method according to claim 4, it is characterised in that the power of the dc source on second target is 15W。
- 6. preparation method according to claim 1, it is characterised in that the power of the dc source on first target is 100~500 W.
- 7. preparation method according to claim 6, it is characterised in that the power of the dc source on first target is 300~500W.
- 8. preparation method according to claim 1, it is characterised in that the total pressure for controlling sputter gas is 1~2.5 Pa, Partial pressure of oxygen is 20-40%.
- 9. the preparation method according to Claims 2 or 3, it is characterised in that first target or/and the second target and base The distance at bottom is 7~20 cm；Initial substrate temperature is room temperature, and base reservoir temperature is below 80 DEG C at the end of deposition；Background vacuum Less than 10-4 Pa。
- 10. cobalt oxide films prepared by a kind of method according to any one of claim 1-9, it is characterised in that described Co in cobalt oxide films2+、Co3+Mol ratio with doped metal ion is（50~100）:（50~100）:（0~5）.
- 11. cobalt oxide films according to claim 10, it is characterised in that the cobalt oxide films thickness be 5~ 20 nm, it is seen that light transmission rate reaches 50~80%.
- A kind of 12. preparation method of perovskite solar cell, it is characterised in that including：Sunk successively in electrically conducting transparent substrate Product cobalt oxide films, perovskite light absorbing layer, electron transfer layer and back electrode, wherein the cobalt oxide films are using power Profit requires that the method any one of 1 to 9 is made.
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