CN109830545A - A kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery - Google Patents
A kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery Download PDFInfo
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Abstract
The present invention provides a kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery.The surface modifying material is ZnMoOxFilm, wherein 3 < x < 4, and the ZnMoOxThe surface work function of film is 4.3eV~4.86eV.Preparing aluminum-doped zinc oxide transparent conducting films surface modifying material provided by the invention, with the tunable surface work function of stable wide scope (3.83eV-4.86eV), solve the problems, such as that the process for modifying surface for increasing ZnO:Al work function at present is difficult to form stability of the stable surface texture to guarantee surface work function.With this ZnMoOxThe modified preparing aluminum-doped zinc oxide transparent conducting films in surface as positive electrode amorphous silicon unijunction thin-film solar cells with the open-circuit voltage of 0.89V, 0.61 fill factor and 6.54% photoelectric conversion efficiency.
Description
Technical field
The disclosure belongs to photoelectron technical field more particularly to a kind of aluminum-doped zinc oxide films surface modifying material, system
Preparation Method and battery.
Background technique
Transparent conductive oxide film is a kind of very crucial material in film light electronic device, has both been had good
Electric conductivity, and there is very high transmitance in visible-range.These characteristics make its liquid crystal display, electroluminescent device,
It has a wide range of applications in the opto-electronic devices such as thin-film solar cells.Fluorine-doped tin oxide (SnO2: F) and tin-doped indium oxide
(In2O3: Sn) it is the transparent conductive oxide film material having been commercialized currently being widely used.Both have superior
Electric property, but there are still defects to hinder their applications in next-generation opto-electronic device.Firstly, In2O3: Sn by
In being used as raw material using rare indium mineral in nature, there are raw material supply it is unsustainable with cost of material is high asks
Topic.Secondly, SnO2: F and In2O3: Sn there are problems that easily being restored by hydrogen plasma, can plasma enhanced chemical
The performance of the thin film silicon solar cell of gas-phase deposition preparation has a negative impact；The metal In restored by hydrogen plasma
Or Sn ion or atom can be diffused into optical absorbing layer and deteriorate device performance.
Aluminium-doped zinc oxide (ZnO:Al) transparent conductive film due to crustal elements content abundant, low raw material at
Sheet, nontoxicity have many advantages, such as high stability in hydrogen plasma environment, become substitution SnO2: F and In2O3: Sn's is strong
Candidate.But with SnO2: F and In2O3: Sn is compared, deficiency ZnO:Al low there are surface work function value.Depend on material
The measurement method of preparation method and work function, the surface work function value of current published ZnO:Al 3.7eV to 4.62eV it
Between.SnO2: the surface work function value of F is even higher for 4.50eV, and In2O3: the surface work function value of Sn is arrived in 4.3eV
Between 4.84eV.Therefore, when ZnO:Al is applied to the opto-electronic devices such as light emitting diode or solar battery as anode material
When, understand injection and the extraction process in ZnO:Al and p-type functional layer interface formation potential barrier obstruction holoe carrier and deteriorates device
Part performance.
There are mainly three types of the methods of the existing surface work function that ZnO:Al can be improved.First is that surface clean, such as acetone
Surface work function can be improved about 3% by the pollution of removal surface carbon with the deionized water cleaning surface ZnO:Al.For another example argon ion
Sputter clean can also effectively remove surface carbon pollution and surface work function is improved about 6%.Second is that using ultraviolet-aided ozonisation
Processing or oxygen plasma treatment, by changing the ratio of surface composition element and forming active oxygen radical for surface work content
Number improves about 13%.But both methods is only capable of ZnO:Al surface work function being increased to about 4.3eV.Third is that using organic
Surface modifying material forms specific molecular structure or dipole on the surface ZnO to regulate and control surface work function.Such method can be big
Amplitude improves ZnO:Al surface work function to about 5.6eV.Although method two and three significantly improves ZnO:Al surface work function,
Modified surface composition and structure are easy variation rapidly under ambient enviroment causes surface work function to decline.Therefore, how
While improving ZnO:Al surface work function and guarantee that the stability of surface work function is that this field research staff is urgently to be resolved
Problem.
Summary of the invention
(1) technical problems to be solved
The existing technology for increasing ZnO:Al surface work function, it is difficult to form stable surface composition and structure to guarantee table
The stability of face work function.If the ZnO:Al of these technical treatments is applied in opto-electronic device, due to surface work content
Several unstability will lead to the problems such as deterioration of device performance.
(2) technical solution
One aspect of the present invention provides a kind of surface modifying material of ZnO:Al transparent conductive film, the surface modifying material
For ZnMoOxFilm, wherein 3 < x < 4, and the ZnMoOxThe surface work function of film is 4.3eV~4.86eV.Wherein, institute
State ZnMoOxFilm with a thickness of 28~32nm.The ZnMoOxThe surface roughness of film is less than 3nm.
The ZnMoO of ZnO:Al provided by the inventionxSurface modifying material passes through ZnO and MoOxBetween reaction formation have
The ZnMoO of specific crystal structurexAlloy cpd realizes the tunable surface work of stable wide scope (3.83eV-4.86eV)
Function, solve the existing process for modifying surface for increasing ZnO:Al work function be difficult to be formed stable surface composition and structure with
The problem of guaranteeing the stability of surface work function.
Another aspect of the present invention additionally provides a kind of preparation of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material
Method, which is characterized in that the described method includes: step A: preparing aluminium-doped zinc oxide transparent conductive thin on a glass substrate
Film cleans the surface of the transparent conductive film；Step B: preparing aluminum-doped zinc oxide transparent conducting films after cleaning
It is upper to grow Electrochromic Molybdenum Oxide Coatings using vacuum vapor deposition method, it obtains positioned at the preparing aluminum-doped zinc oxide transparent conducting films surface
ZnMoOxFilm.
Wherein, the preparation method of preparing aluminum-doped zinc oxide transparent conducting films described in step A includes: Organometallic Chemistry
Vapour deposition process, magnetron sputtering method, sol-gel method, pulsed laser deposition and spray pyrolysis.
The preparation method of Electrochromic Molybdenum Oxide Coatings described in step B, cold boiler model Sanvac RD-1250R are described
The voltage for being applied to the tungsten boat both ends of cold boiler is 14-16V.
The method also includes: step C: carrying out air atmosphere heat treatment to the product after step B, obtains being located at described
The ZnMoO after air atmosphere is heat-treated on preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
ZnMoO after being heat-treated by air atmospherexFilm, the modified surface work function is up to 4.86eV；By
Stable surface composition is obtained in formation crystalline phase, guarantees the stability of surface work function.
The method also includes: step D: carrying out nitrogen atmosphere heat treatment to the product after step C, obtains being located at described
The ZnMoO after atmosphere and nitrogen atmosphere heat treatment on preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
ZnMoO after being heat-treated by nitrogen atmospherexFilm, the modified surface work function up to 4.85eV, and
It is relatively stable under ambient enviroment.
Wherein, the preparation method of preparing aluminum-doped zinc oxide transparent conducting films described in step A includes: Organometallic Chemistry
Vapour deposition process, magnetron sputtering method, sol-gel method, pulsed laser deposition and spray pyrolysis.
The vacuum degree for the cold boiler that vacuum vapor deposition method described in the step B uses is 4.1-4.5 × 10-4Pa, institute
The film growth rate for stating Electrochromic Molybdenum Oxide Coatings is 0.08-0.12nm/s.
The step C includes: that the product after step B is put into infrared lamp heating furnace chamber, in air atmosphere, with
The rate of heat addition of 2.4 DEG C/s is heated to 350 DEG C -400 DEG C, and keeps the temperature 5min, then naturally cools to furnace lower than 80 DEG C.
The step D includes: that the product after step C is put into infrared lamp heating furnace chamber, with 0.9-1.1L/min
Flow velocity nitrogen is imported into heating furnace, be heated to 400 DEG C with the rate of heat addition of 2.4 DEG C/s, and keep the temperature 5min-60min, then
It naturally cools to furnace lower than 80 DEG C.
Another aspect of the invention additionally provides a kind of thin-film solar cells, and the thin-film solar cells includes amorphous silicon
Thin-film solar cells, perovskite thin film solar battery and organic thin film solar cell, which is characterized in that the battery pack
Include preparing aluminum-doped zinc oxide transparent conducting films surface modifying material described above.
(3) beneficial effect
Preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, preparation method and thin film solar provided by the invention
Battery at least has the advantages that one of them or in which a part:
(1) ZnMoO prepared byxThe surface work function that material has wide scope (3.83eV-6.86eV) tunable.
(2) ZnMoO prepared byxMaterial is heat-treated to form crystalline phase by air atmosphere, further increases surface work content
While number, the stability that stable surface composition and structure guarantee surface work function is obtained.
(3) ZnMoO prepared byxPolycrystalline material can be realized low thin by nitrogen atmosphere heat treatment generation Lacking oxygen donor state
Film resistance, to reduce the series resistance in device.
(4) ZnMoO prepared byxPolycrystalline material can be realized by accurately controlling the content of Mo to surface work function and light number
The regulation of the performance parameters such as constant (specific refractivity and extinction coefficient).
(5) ZnMoO prepared byxModified ZnO:Al transparent conductive substrate can be applied not only to amorphous silicon, perovskite
Or the thin-film solar cells such as organic, the field of optoelectronic devices such as optical detector and organic photodiode can also be applied to.
Detailed description of the invention
Fig. 1 (a) is the surface Scanning Electron microscope figure of comparative example 1 in embodiment 7 provided by the invention, and scale is in figure
200nm；
Fig. 1 (b) is the surface Scanning Electron microscope figure of ZMO1 in embodiment 7 provided by the invention, and scale is in figure
200nm；
Fig. 1 (c) is the surface Scanning Electron microscope figure of ZMO2 in embodiment 7 provided by the invention, and scale is in figure
200nm；
Fig. 1 (d) is the surface Scanning Electron microscope figure of ZMO3 in embodiment 7 provided by the invention, and scale is in figure
200nm；
Fig. 2 (a) is Zn element, the Al for the ZnO:Al transparent conductive film that several surface modifying materials are modified in embodiment 8
Element, Mo element, O element are along depth of material distribution map；
Fig. 2 (b) is the O element and Mo for the ZnO:Al transparent conductive film that several surface modifying materials are modified in embodiment 8
The opposite variation of the ratio (O/Mo element ratio) of element is along depth of material distribution map；
Fig. 3 is the X-ray diffractogram for the ZnO:Al transparent conductive film that several surface modifying materials are modified in embodiment 9
Spectrum, wherein ZMO0 is conventional x-ray diffraction map, and ZMO1, ZMO2 and ZMO3 are glancing X-ray diffraction map, buergerite
Type ZnO is the standard diagram of JCPDS card No.36-1451；
Fig. 4 is that the ultraviolet-visible-for the ZnO:Al transparent conductive film that several surface modifying materials are modified in embodiment 10 is close
Infrared transmittance graph figure；
Fig. 5 is the Secondary- for the ZnO:Al transparent conductive film that several surface modifying materials are modified in embodiment 11
The ultraviolet photoelectron spectroscopy figure in the region electron cut-off.
Fig. 6 (a) is the short-circuit current density (J of the amorphous silicon unijunction thin-film solar cells prepared in embodiment 13sc) figure；
Fig. 6 (b) is the open-circuit voltage (V of the amorphous silicon unijunction thin-film solar cells prepared in embodiment 13oc) figure；
Fig. 6 (c) is fill factor (FF) figure of the amorphous silicon unijunction thin-film solar cells prepared in embodiment 13；
Fig. 6 (d) is photoelectric conversion efficiency (η) figure of the amorphous silicon unijunction thin-film solar cells prepared in embodiment 13；
Fig. 6 (e) is the series resistance (R of the amorphous silicon unijunction thin-film solar cells prepared in embodiment 13s) figure；
Fig. 6 (f) is the parallel resistance (R of the amorphous silicon unijunction thin-film solar cells prepared in embodiment 13sh) figure.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in more detail.
The present invention provides a kind of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, and the surface modifying material is
ZnMoOx(3 < x < 4) film, and the ZnMoOxThe work function of film is 4.3eV~4.86eV.Wherein, the ZnMoOx
Film with a thickness of 28~32nm.The ZnMoOxThe surface roughness of film is less than 3nm.
The preparing aluminum-doped zinc oxide transparent conducting films surface modifying material provided through the invention has stable wide scope
The surface work function that (3.83eV-4.86eV) is tunable.It solves the existing technology for increasing ZnO:Al surface work function to be difficult to
The problem of forming stability of the stable surface composition to guarantee surface work function.
The present invention also provides a kind of preparation method of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, features
It is, which comprises step A: preparing preparing aluminum-doped zinc oxide transparent conducting films on a glass substrate, to described transparent
The surface of conductive film is cleaned；Step B: vacuum evaporation is used on preparing aluminum-doped zinc oxide transparent conducting films after cleaning
Method grows Electrochromic Molybdenum Oxide Coatings, obtains the ZnMoO positioned at the preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
The ZnMoO that preparation method A and B are prepared through the inventionxFilm, since surface composition is inorganic modified material
Material, it is relatively stable under ambient enviroment.
The method also includes: step C: carrying out air atmosphere heat treatment to the product after step B, obtains being located at described
The ZnMoO after air atmosphere is heat-treated on preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
ZnMoO after being heat-treated by air atmospherexFilm, surface work function is up to 4.86eV, and in ambient enviroment
Under it is relatively stable.
The method also includes: step D: carrying out nitrogen atmosphere heat treatment to the product after step C, obtains being located at described
The ZnMoO after atmosphere and nitrogen atmosphere heat treatment on preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
It should be noted that the ZnMoO after atmosphere and nitrogen atmosphere heat treatment hereinxFilm refers to, by upper
The ZnMoO that step B is obtained in textxFilm is heat-treated after being heat-treated twice by the air atmosphere of first time, then
By the product after the air atmosphere heat treatment by first time after the heat treatment of secondary nitrogen atmosphere, it is big to obtain the warp
ZnMoO after gas and nitrogen atmosphere heat treatmentxFilm.
ZnMoO after being heat-treated again by nitrogen atmospherexFilm, surface work function are realized lower up to 4.85eV
Film resistor.
Wherein, the preparation method of preparing aluminum-doped zinc oxide transparent conducting films described in step A includes: Organometallic Chemistry
Vapour deposition process, magnetron sputtering method, sol-gel method, pulsed laser deposition and spray pyrolysis.
The vacuum degree for the cold boiler that vacuum vapor deposition method described in the step B uses is 4.1-4.5 × 10-4Pa, institute
The film growth rate for stating Electrochromic Molybdenum Oxide Coatings is 0.08-0.12nm/s.
The step C includes: that the product after step B is put into infrared lamp heating furnace chamber, in air atmosphere, with
The rate of heat addition of 2.4 DEG C/s is heated to 350 DEG C -400 DEG C, and keeps the temperature 5min, then naturally cools to furnace lower than 80 DEG C.
The step D includes: that the product after step C is put into infrared lamp heating furnace chamber, with 0.9-1.1L/min
Flow velocity nitrogen is imported into heating furnace, be heated to 400 DEG C with the rate of heat addition of 2.4 DEG C/s, and keep the temperature 5min-60min, then
It naturally cools to furnace lower than 80 DEG C.
The present invention also provides a kind of thin-film solar cells, the thin-film solar cells includes the amorphous silicon membrane sun
Energy battery, perovskite thin film solar battery and organic thin film solar cell, which is characterized in that the battery includes institute above
The preparing aluminum-doped zinc oxide transparent conducting films surface modifying material stated.
In the following, being illustrated to be further illustrated to technical solution of the present invention by following specific examples
Illustrate:
Embodiment 1:
The present embodiment provides a kind of amorphous state ZnMoOx(3 < x < 4) film is as preparing aluminum-doped zinc oxide transparent conducting films
Surface modifying material.The ZnMoOxThe surface work function of film is 4.3eV.The ZnMoOxThe thickness 28-32nm of film.It is described
ZnMoOxThe surface roughness of film is 1.9nm.
Embodiment 2:
The present embodiment provides a kind of polycrystalline ZnMoOx(3 < x < 4) film is as preparing aluminum-doped zinc oxide transparent conducting films
Surface modifying material.The ZnMoOxThe surface work function of film is 4.86eV.The ZnMoOxFilm with a thickness of 28-32nm.It is described
ZnMoOxThe surface roughness of film is 1.5nm.
Embodiment 3:
The present embodiment provides a kind of low resistance polycrystalline ZnMoOx(3 < x < 4) film is as aluminium-doped zinc oxide transparent conduction
The surface modifying material of film.The ZnMoOxThe surface work function of film is 4.85eV.The ZnMoOxFilm with a thickness of 32nm.
The ZnMoOxThe surface roughness of film is 2.6nm.
Embodiment 4:
The present embodiment provides a kind of preparation methods of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, under
Column step A and B are obtained:
Step A: it is thin that aluminium-doped zinc oxide ZnO:Al electrically conducting transparent is prepared by sol-gel method on a glass substrate
Film, the performance parameter for the ZnO:Al transparent conductive film being prepared is referring to table 1, wherein film resistor is by four probe resistances
The average value that test equipment is measured in 6 different locations of sample surfaces.σrmsRoughness is by atomic force microscopy Electronic Speculum (Atomic
Force Morphology) root-mean-square value of film surface bumps profile that measures.Then to the surface of the transparent conductive film
It is cleaned, which is cleaned by ultrasonic in alcohol, acetone and alcohol respectively each 10 minutes, finally with drying
It is dried with nitrogen.
1 preparing aluminum-doped zinc oxide transparent conducting films performance parameter table of table
| Transparent conductive film | Thickness (nm) | Resistivity (Ω cm) | Film resistor (Ω/sq) | Roughness σrms(nm) |
| ZnO:Al | 1500 | 2.34×10-3 | 15.6 | 2.6 |
Step B: molybdenum oxide is grown using vacuum vapor deposition method on preparing aluminum-doped zinc oxide transparent conducting films after cleaning
(MoO3-δ, wherein 0 <, 6 < 1) and film, obtain the ZnMoO positioned at the preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
Specifically, the ZnO:Al transparent conductive film after cleaning is placed in high vacuum evaporation device (model Sanvac RD-
In 1250R).It is evacuated to 4.1-4.5 × 10-4Pa；Tungsten boat both end voltage is slowly increased to about 14-16V, when tungsten boat reddens
When, shield is opened, timing is started simultaneously at, film, chinese raw materials molybdenum oxide powder are deposited with the growth rate of 0.08-0.12nm/s
The weight at end is 0.0060-0.0080g；When film reaches 28-32nm, shield is closed, slowly reduces voltage to 0V；Wait temperature
When degree is reduced near room temperature, sample is taken out, obtains the ZnMoO positioned at the preparing aluminum-doped zinc oxide transparent conducting films surfacex
Film.
Embodiment 5:
The present embodiment provides a kind of preparation methods of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, will pass through
The ZnMoO positioned at the preparing aluminum-doped zinc oxide transparent conducting films surface obtained by the preparation method of embodiment 4xFilm is made
For initial sample, to initial sample implementation steps C: to the ZnMoOxFilm carries out air atmosphere heat treatment, specifically, by this
ZnMoOxFilm is put into infrared lamp heating furnace chamber, in ambient atmosphere atmosphere, is heated to the rate of heat addition of 2.4 DEG C/s
350 DEG C -400 DEG C, and 5min is kept the temperature, then it is lower than 80 DEG C with furnace natural cooling.It obtains being located at the aluminium-doped zinc oxide transparent
The ZnMoO after air atmosphere is heat-treated on conductive film surfacexFilm.
Embodiment 6:
The present embodiment provides a kind of preparation methods of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, will pass through
By the preparation method of embodiment 5 obtain be located at the preparing aluminum-doped zinc oxide transparent conducting films surface through air atmosphere heat
ZnMoO after reasonxFilm, as initial sample, to initial sample implementation steps D: to the ZnMoOxFilm carries out air atmosphere
Heat treatment, specifically, by the ZnMoOxFilm is put into infrared lamp heating furnace chamber, with the flow velocity of 0.9-1.1L/min to heating
N is imported in furnace2, it is heated to keep the temperature 5min-60min after 400 DEG C with the rate of heat addition of about 2.4 DEG C/s, it is then naturally cold with furnace
But it is lower than 80 DEG C.It obtains positioned at the preparing aluminum-doped zinc oxide transparent conducting films surface at through atmosphere and nitrogen atmosphere heat
ZnMoO after reasonxFilm.
Embodiment 7:
The present embodiment using the ZnO:Al transparent conductive film after the cleaning obtained by step A in embodiment 4 as pair
Ratio 1, is denoted as ZMO0, is located at the preparing aluminum-doped zinc oxide transparent conducting films surface for what is obtained by step B in embodiment 4
ZnMoOxFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3.
Pass through scanning electron microscope (SEM) respectively to ZMO0, ZMO1, ZMO2, ZMO3 and obtain surface SEM picture, as a result
As shown in Figure 1.The surface SEM figure that Fig. 1 (a) is the ZMO0 provided in comparative example 1, the surface SEM that Fig. 1 (b) is ZMO1 scheme, Fig. 1
(c) scheme for the surface SEM of ZMO2, the surface SEM that Fig. 1 (d) is ZMO3 schemes.
Referring to Fig. 1, it is seen that several ZnMoOxFilm sample all has a very flat surface, the surface of these samples be by
Nano-grade size crystal grain is constituted.ZMO1, ZMO2, ZMO3 have more tiny than ZMO0 and more evenly crystal grain.ZMO1's and ZMO2
Surface σrmsRoughness ratio ZMO0 is lower, and the surface σ of ZMO3rmsRoughness is slightly above ZMO0.
Embodiment 8:
The present embodiment is located at the preparing aluminum-doped zinc oxide transparent conducting films table for what is obtained by step B in embodiment 4
The ZnMoO in facexFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3.
The measurement along depth of material Elemental redistribution is carried out respectively to ZMO1, ZMO2, ZMO3, as a result as shown in Fig. 2, Fig. 2 (a)
For the Zn element of the modified ZnO:Al transparent conductive film of surface modifying materials several in embodiment 8, Al element, Mo element, O member
Element is along depth of material distribution diagram of element.Fig. 2 (b) is the ZnO:Al electrically conducting transparent that several surface modifying materials are modified in embodiment 8
The opposite variation of the ratio (O/Mo element ratio) of the O element and Mo element of film is along depth of material distribution map.Wherein incite somebody to action
O/Mo element ratio in ZMO1 is set as 1.
As shown in Fig. 2 (a), there is one kind in the range of the surface of ZnO:Al about 30nm thickness and be made of Zn, Mo and O element
Novel substance.This proves ZnMoOxModified layer is formed on the surface of ZnO:Al.As shown in Fig. 2 (b), ZnMoOxO/Mo element in layer
It is more obvious than changing；The O/Mo element ratio of ZMO2 is significantly greater than ZMO1's；This proves to send out in first step air atmosphere heat treatment process
Raw oxidation reaction, increases ZnMoOxOxygen content in layer.The O/Mo element ratio of ZMO3 is slightly less than ZMO2, but is still greater than
ZMO1's；This shows that second step nitrogen atmosphere heat treatment process slightly reduces ZnMoOxOxygen content in layer.
Embodiment 9:
The present embodiment using the ZnO:Al transparent conductive film after the cleaning obtained by step A in embodiment 4 as pair
Ratio 1, is denoted as ZMO0, is located at the preparing aluminum-doped zinc oxide transparent conducting films surface for what is obtained by step B in embodiment 4
ZnMoOxFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3, right
ZMO0, ZMO1, ZMO2, ZMO3 carry out X-ray diffraction test respectively, and measurement result is referring to Fig. 3.
As shown in figure 3, the preferred orientation in apparent (002) direction is presented in ZMO0.ZMO1 is presented and standard wurtzite-type ZnO
Similar map.This shows that ZMO1 should be amorphous state.After the heat treatment of first step air atmosphere, 27 degree on ZMO2 map
Left-right position occurs two and is respectively labeled as X1And X2New diffraction maximum.This proves that air atmosphere heat treatment causes to crystallize, and is formed
New object phase.After the heat treatment of second step nitrogen atmosphere, ZMO3 shows the X almost the same with ZMO21And X2Diffraction maximum
By force.This shows that nitrogen atmosphere heat treatment is not significantly affected to being formed by new object and mutually generate.Element composition according to Fig.2,
Deducibility X1And X2Diffraction maximum corresponding to new object mutually should be with ZnMoOxCertain crystalline phase it is related.
Embodiment 10:
The present embodiment using the ZnO:Al transparent conductive film after the cleaning obtained by step A in embodiment 4 as pair
Ratio 1, is denoted as ZMO0, is located at the preparing aluminum-doped zinc oxide transparent conducting films surface for what is obtained by step B in embodiment 4
ZnMoOxFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3, right
ZMO0, ZMO1, ZMO2 and ZMO3 carry out ultraviolet-visible-near-infrared transmissivity measurement respectively, and measurement result is referring to fig. 4.
As shown in figure 4, all films all show the transmitance higher than 85% in 400-1500nm wave-length coverage；?
The ZnMoO that the surface ZnO:Al is formedxModified layer is almost without the transmitance for reducing ZnO:Al substrate.But 350-400nm's
Short wavelength region, ZMO2 and ZMO3 show the transmitance lower than ZMO0 and ZMO1.This shows ZnMoOxThe photonic band gap of material
Width slightly becomes smaller after air atmosphere heat treatment.This may be due to generating X in Fig. 3 in air atmosphere heat treatment process1
And X2The corresponding ZnMoO of diffraction maximumxCrystalline phase.In general, a kind of crystalline phase of material shows the photonic band gap smaller than amorphous phase
Width.In addition, the transmitted spectrum of all films shows wavy shape with the increase of wavelength.This is more by different position phases
Caused by Fabry-Perot (Fabry-P é rot) interference effect between light beam.The flat surfaces of these films cause in exit end
Form the light that many directions are identical but position is mutually different.
Embodiment 11:
The present embodiment using the ZnO:Al transparent conductive film after the cleaning obtained by step A in embodiment 4 as pair
Ratio 1, is denoted as ZMO0, is located at the preparing aluminum-doped zinc oxide transparent conducting films surface for what is obtained by step B in embodiment 4
ZnMoOxFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3, right
The ultraviolet photoelectron that ZMO0, ZMO1, ZMO2, ZMO3 carry out the region Secondary-electron cut-off respectively is capable of measuring,
Measurement result is referring to Fig. 5.Fig. 5 is the Secondary- of the modified ZnO:Al transparent conductive film of ZMO0, ZMO1, ZMO2, ZMO3
The ultraviolet photoelectron spectroscopy figure in the region electron cut-off.
As shown in figure 5, the ZnMoO formed on the surface ZnO:AlxAfter modified layer, Secondary-electron cut-
The edge off is significantly mobile to high-energy direction, shows that surface work function is obviously improved.
Embodiment 12:
The present embodiment using the ZnO:Al transparent conductive film after the cleaning obtained by step A in embodiment 4 as pair
Ratio 1, is denoted as ZMO0, is located at the preparing aluminum-doped zinc oxide transparent conducting films surface for what is obtained by step B in embodiment 4
ZnMoOxFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3.It is right
ZMO0, ZMO1, ZMO2, ZMO3 carry out work function value measurement respectively, and measurement result is shown in table 2.
2 ZMO0, ZMO1, ZMO2 and ZMO3 work function value of table
| Sample | ZMO0 | ZMO1 | ZMO2 | ZMO3 |
| Work function (eV) | 3.83 | 4.30 | 4.86 | 4.85 |
As seen from the results in Table 2, the surface work function value of ZMO0 is 3.83eV.The ZnO of this and radio-frequency magnetron sputter method preparation:
The surface work function of Al transparent conductive film is very close.The surface work function of amorphous ZMO1 increases by 12% with respect to ZMO0.
In the embodiment of the present disclosure 4 during step B, in vacuum deposition MoO3-δIn thin-film process, MoO3-δShape is reacted with the ZnO on surface
At amorphous ZnMoOx。MoO3-δWith the up to work function of 6.86eV.Due to high work function MoO3-δBe incorporated to so that ZMO1
Realize work function more higher than ZMO0.Surface work function by the ZMO2 of air atmosphere recrystallization annealing increases with respect to ZMO0
27%, realize the high work content numerical value of 4.86eV.This, which reflects, forms certain ZnMoO in air atmosphere heat treatment processxCrystalline phase
So that surface work function is further promoted.In addition, being heat-treated by nitrogen atmosphere, the surface work function of ZMO3 is almost with respect to ZMO2
Do not change.This proves that being heat-treated promoted surface work function by air atmosphere has preferable stability.This may be
Since the ZMO2 of crystallization has firm surface texture, that is, orderly atomic arrangement and relatively strong bonding stable to guarantee
Surface composition and the stability for improving surface work function.Further, it referring to Fig. 3, is heat-treated according to nitrogen atmosphere in embodiment 9
New object formed in air atmosphere heat treatment process is not generated mutually and is significantly affected, ZMO3 is may infer that still and has and is similar
The firm surface crystal structure of ZMO2 and guarantee stable surface composition.It could therefore be concluded that the surface work function of ZMO3
With preferable stability.In addition, the surface work function value of ZMO2 and ZMO3 has reached or even surmounts SnO2: F and In2O3: Sn's
Surface work function is horizontal.
Embodiment 13:
The present embodiment using the ZnO:Al transparent conductive film after the cleaning obtained by step A in embodiment 4 as pair
Ratio 1, is denoted as ZMO0, is located at the preparing aluminum-doped zinc oxide transparent conducting films surface for what is obtained by step B in embodiment 4
ZnMoOxFilm is denoted as ZMO1, the ZnMoO after air atmosphere is heat-treated that will be obtained by embodiment 5xFilm is denoted as
ZMO2, the ZnMoO after atmosphere and nitrogen atmosphere heat treatment that will be obtained by embodiment 6xFilm is denoted as ZMO3.Respectively
Using ZMO0, ZMO1, ZMO2, ZMO3 modified ZnO:Al transparent conductive substrate as positive electrode, amorphous silicon (a-Si:H) is made
Unijunction thin-film solar cells.The amorphous silicon unijunction thin-film solar cells successively includes: ZnO:Al electrically conducting transparent from top to bottom
Substrate, ZnMoOxSurface reforming layer, p-i-na-Si:H absorbed layer, boron doping zinc oxide (ZnO:B) back-scattering layer, aluminum metal electricity
Pole.Wherein prepared by p-i-n a-Si:H absorbed layer using plasma enhanced chemical vapor deposition method；ZnO:B back-scattering layer
(thickness 1500nm) is prepared using Metalorganic Chemical Vapor Deposition.
Performance parameter measurement is carried out to prepared amorphous silicon unijunction thin-film solar cells respectively, obtained result is as schemed
Shown in 6 (a)~Fig. 6 (f).Fig. 6 (a) is the short-circuit current density (J of prepared amorphous silicon unijunction thin-film solar cellssc),
Fig. 6 (b) is the open-circuit voltage (V of prepared amorphous silicon unijunction thin-film solar cellsoc), Fig. 6 (c) is prepared amorphous silicon
The fill factor (FF) of unijunction thin-film solar cells, Fig. 6 (d) are the light of prepared amorphous silicon unijunction thin-film solar cells
Photoelectric transformation efficiency (η), Fig. 6 (e) are the series resistance (R of prepared amorphous silicon unijunction thin-film solar cellss), Fig. 6 (f) is
Parallel resistance (the R of prepared amorphous silicon unijunction thin-film solar cellssh)。
According to result it is found that realizing the J bigger than ZMO0 and ZMO1 using ZMO2 and ZMO3sc.This may be due to atmosphere
Atmosphere heat treatment generates crystallization and increases ZnMoOxThe refraction coefficient of modified layer, thus in transparent conductive substrate and p-type a-Si:H
Better index matching is formed at bed boundary, is increased light absorption and is increased Jsc.Highest J is obtained using ZMO2sc, but shape
At highest series resistance (Rs), minimum fill factor (FF) is resulted in, so that compared with ZMO0 and ZMO1, the light of battery
(function is not apparent from promotion to photoelectric transformation efficiency.R is greatly lowered using ZMO3s, realize the open-circuit voltage (V of highest 0.89Voc) and
0.61 FF, to realize highest η (6.54%).RsDecline be due to nitrogen atmosphere be heat-treated reduce ZMO3 resistivity.
The decline of ZMO3 resistivity is promoted due to generating the Lacking oxygen donor state of ionization in nitrogen atmosphere heat treatment process
ZnMoOxCarrier concentration in modified layer.Therefore, ZMO3 surface reforming layer not only improves VocIt is effectively facilitated carrier pumping
Process is taken, and improves FF, to obtain highest incident photon-to-electron conversion efficiency.In addition, using ZnMoOxSurface reforming layer is to device
Parallel resistance (Rsh) generate have little effect on.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, which is characterized in that the surface modifying material is
ZnMoOxFilm, wherein 3 < x < 4, and the ZnMoOxThe surface work function of film is 4.3eV~4.86eV.
2. surface modifying material according to claim 1, which is characterized in that the ZnMoOxFilm with a thickness of 28~
32nm。
3. surface modifying material according to claim 1, which is characterized in that the ZnMoOxThe surface roughness of film is small
In 3nm.
4. a kind of preparation method of preparing aluminum-doped zinc oxide transparent conducting films surface modifying material, which is characterized in that the method
Include:
Step A: preparing preparing aluminum-doped zinc oxide transparent conducting films on a glass substrate, to the surface of the transparent conductive film
It is cleaned；
Step B: Electrochromic Molybdenum Oxide Coatings are grown using vacuum vapor deposition method on preparing aluminum-doped zinc oxide transparent conducting films after cleaning, are obtained
To the ZnMoO for being located at the preparing aluminum-doped zinc oxide transparent conducting films surfacexFilm.
5. according to the method described in claim 4, it is characterized in that, the method also includes step C: to the production after step B
Product carry out air atmosphere heat treatment, obtain positioned at the preparing aluminum-doped zinc oxide transparent conducting films surface at through air atmosphere heat
ZnMoO after reasonxFilm.
6. according to the method described in claim 5, it is characterized in that, the method also includes step D: to the production after step C
Product carry out nitrogen atmosphere heat treatment, obtain positioned at the preparing aluminum-doped zinc oxide transparent conducting films surface through air atmosphere, with
And the ZnMoO after nitrogen atmosphere heat treatmentxFilm.
7. according to the method described in claim 4, it is characterized in that, the vacuum that vacuum vapor deposition method described in the step B uses
The vacuum degree of evaporator is 4.1-4.5 × 10-4Pa, the film growth rate of the Electrochromic Molybdenum Oxide Coatings are 0.08-0.12nm/s.
8. according to the method described in claim 4, it is characterized in that, the step C includes: to be put into the product after step B
In infrared lamp heating furnace chamber, in air atmosphere, 350 DEG C -400 DEG C are heated to the rate of heat addition of 2.4 DEG C/s, and keep the temperature
Then 5min is naturally cooled to furnace lower than 80 DEG C.
9. according to the method described in claim 4, it is characterized in that, the step D includes: to be put into the product after step C
In infrared lamp heating furnace chamber, nitrogen is imported into heating furnace with the flow velocity of 0.9-1.1L/min, with the rate of heat addition of 2.4 DEG C/s
400 DEG C are heated to, and keeps the temperature 5min-60min, is then naturally cooled to furnace lower than 80 DEG C.
10. a kind of thin-film solar cells, the thin-film solar cells includes that amorphous silicon thin-film solar cell, perovskite are thin
Film solar cell and organic thin film solar cell, which is characterized in that the battery includes any one of claims 1 to 3
The preparing aluminum-doped zinc oxide transparent conducting films surface modifying material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030066519A1 (en) * | 2001-09-28 | 2003-04-10 | Wachsman Eric D. | Solid state potentiometric gaseous oxide sensor |
| CN103660418A (en) * | 2012-09-20 | 2014-03-26 | 海洋王照明科技股份有限公司 | Conducting film, and preparation method and application thereof |
| CN104210167A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conductive film, preparation method and applications thereof |
| US20150279498A1 (en) * | 2014-03-27 | 2015-10-01 | Samsung Electronics Co., Ltd. | Transparent conductive thin film electrodes, electronic devices and methods of producing the same |
| CN105185843A (en) * | 2014-06-18 | 2015-12-23 | 华东师范大学 | Strippable any imaging transparent conductive thin film and applications thereof |
| CN105591072A (en) * | 2016-02-29 | 2016-05-18 | 陕西科技大学 | Negative electrode piece of alpha-ZnMoO4 lithium ion battery and preparation method of negative electrode piece |
| US20180350529A1 (en) * | 2017-06-05 | 2018-12-06 | National Cheng Kung University | Method of fabricating solar cell |
-
2019
- 2019-02-14 CN CN201910116789.XA patent/CN109830545B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030066519A1 (en) * | 2001-09-28 | 2003-04-10 | Wachsman Eric D. | Solid state potentiometric gaseous oxide sensor |
| CN103660418A (en) * | 2012-09-20 | 2014-03-26 | 海洋王照明科技股份有限公司 | Conducting film, and preparation method and application thereof |
| CN104210167A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conductive film, preparation method and applications thereof |
| US20150279498A1 (en) * | 2014-03-27 | 2015-10-01 | Samsung Electronics Co., Ltd. | Transparent conductive thin film electrodes, electronic devices and methods of producing the same |
| CN105185843A (en) * | 2014-06-18 | 2015-12-23 | 华东师范大学 | Strippable any imaging transparent conductive thin film and applications thereof |
| CN105591072A (en) * | 2016-02-29 | 2016-05-18 | 陕西科技大学 | Negative electrode piece of alpha-ZnMoO4 lithium ion battery and preparation method of negative electrode piece |
| US20180350529A1 (en) * | 2017-06-05 | 2018-12-06 | National Cheng Kung University | Method of fabricating solar cell |
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