CN103938156B - A kind of bismuth ferrite thin film of europium doping and its preparation method and application - Google Patents
A kind of bismuth ferrite thin film of europium doping and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of europium doping bismuth ferrite thin film, it include with nickel acid lanthanum be cushion silicon substrate and composition formula for Bi1-xEuxFeO3The target of (0≤x≤0.07), target material deposition is on substrate.The preparation method that the invention also discloses the bismuth ferrite thin film of europium doping, cleans substrate, is placed in coating chamber by target and substrate, regulates pressure to 5 × 10-4Below Pa.Substrate is made to be warming up to 700 DEG C with 10 DEG C per minute；Adjustment makes sputtering pressure be 10Pa；Keep 10 minutes under temperature 700 DEG C, oxygen pressure 10Pa.Adjustment makes substrate reverse, and target rotates forward；The distance of substrate and target is 6cm.Carry out thin film deposition 60min with pulse laser, be incubated 30min.Lower the temperature with the speed of 20 DEG C per minute, obtain the bismuth ferrite thin film of europium doping to 200 DEG C of taking-ups.The preparation method course of reaction of the present invention is easily controllable, and raw material is easy to get.The crystal property of the bismuth ferrite thin film of europium of the present invention doping, electric leakage performance substantially improve, and optical band gap diminishes, and improves BiFeO3The photovoltaic performance of thin film, is with a wide range of applications.
Description
Technical field
The present invention relates to ferrum electricity and photovoltaic material technical field, the bismuth ferrite (BiFeO that a kind of rare earth elements europium (Eu) of concrete proposition is adulterated3) thin film and its preparation method and application.
Background technology
Solar energy is a kind of particularly important regenerative resource.At present, it is possible to what be used as solar energy materials mainly has several materials such as silicon, III-V, CIGS (CIGS), dye sensitization, polymer.Silica-based solar cell is large-scale production, but its opto-electronic conversion mechanism determines and only has the light that energy exceedes band gap could produce electric current, which results in the difficult problem that solar energy converts: little band-gap energy absorbs more multi-photon, produces bigger electric current but undertension；And the big band-gap energy bigger voltage electric current of generation is limited, major part solar photon can not be absorbed, thus conversion efficiency is also difficult to obtain very big raising.
Ferroelectric is a kind of material with spontaneous polarization, and in certain temperature range, a kind of material that its spontaneous polarization dipole moment can change with external electric field direction.Most of ferroelectric materials have semiconductive and ferroelectricity concurrently, the photoelectric conversion capacity that ferroelectric material has, high output photovoltage, electric field regulate and control the characteristic of photovoltaic so that it is have broad application prospects in ferrum power production photovoltaic battery, CD-ROM driver, optical sensor etc..Ferroelectric spontaneous polarization is attractive for solar cell application, and because the positive charge and negative charge being absorbed generation by light has the conatus being separated from each other, this makes them be easier to by Efficient Collection.Regrettably, being used in photovoltaic art at ferroelectric material and face two severe problems: one, ferroelectric material band gap is bigger than normal.Even if can with minimum bismuth ferrite (BiFeO in ferroelectric material3), its band gap has also reached 2.8eV.Therefore, existing ferroelectric material generally only absorbs the composition a fraction of high-energy photon of solar spectrum.Its two, thin film crystallization is second-rate, causes that thin film easily leaks electricity.
Summary of the invention
The defects such as, thin film easily electric leakage big for prior art ferroelectric material band gap, the present invention provides the bismuth ferrite (BiFeO that a kind of rare earth elements europium (Eu) is adulterated3) thin film and preparation method thereof.It is capable of the ferrum electricity bismuth ferrite (BiFeO that preparation can be obviously improved with reduction and thin film crystallization quality according to the present invention3) thin film, thus improving the photovoltaic performance of ferroelectric material.By thin film prepared by this method, its energy gap is 2.6eV.Adopting pulsed laser deposition at nickel acid lanthanum as preparing thin film on the silicon substrate of cushion in the present invention, raw materials used cost is low, simple experiment, effectively can uniformly be mixed by rare-earth europium element, obtain even compact thin film, and surface average roughness is about 2.0nm.
According to the first aspect of the invention, the present invention proposes the bismuth ferrite thin film of a kind of europium doping, and including substrate and target, described target material deposition is over the substrate；Wherein, the silicon substrate that described substrate is is cushion with nickel acid lanthanum, described target composition formula is Bi1-xEuxFeO3, 0≤x≤0.07.According to actual concrete condition, x=0,0.03,0.05 or 0.07.
According to the second aspect of the invention, the preparation method that the present invention proposes the bismuth ferrite thin film of above-mentioned europium doping, the Bi of different Eu elemental constituent is prepared by traditional solid phase reaction method1-xEuxFeO3Sputtering target material, then utilizes pulsed laser deposition to do at nickel acid lanthanum (composition formula is LaNiO3) and prepares corresponding Bi on silicon (symbol of element the is Si) substrate of cushion1-xEuxFeO3Thin film.Preparation method of the present invention specifically includes following steps:
A) pre-preparation
The Bi being 99.99% with purity1-xEuxFeO3As target, wherein 0≤x≤0.07；The silicon substrate of cushion is made as substrate using nickel acid lanthanum；
Described substrate is cleaned, described target and described substrate are positioned in coating chamber, regulate coating chamber pressure to 5 × 10-4Below Pa.
Wherein, the substrate of selection is the silicon substrate that nickel acid lanthanum makes cushion, by the effect of cushion, it is possible to make thin film be grown in well on substrate.
B) preparation of the bismuth ferrite thin film of europium doping
To described silicon；Described substrate is made to be warming up to 700 DEG C with 10 DEG C per minute；Being filled with the oxygen that purity is 99.99%, adjusting gas flow makes sputtering pressure be 10Pa；Temperature 700 DEG C, keep 10 minutes when oxygen pressure 10Pa；
Described substrate reverses, and described target rotates forward；The distance regulating described substrate and described target is 6cm；
Arranging pulse laser, making laser energy is 200mJ, and laser frequency is 10Hz；
Opening described pulse laser and carry out thin film deposition, sedimentation time is 60min；Then 30min it is incubated；
Lower the temperature with the speed of 20 DEG C per minute, take out the film sample that deposition obtains during to 200 DEG C, obtain the bismuth ferrite thin film of described europium doping.
Wherein, by making substrate temperature 700 DEG C, keep substrate 10 minutes when oxygen pressure 10Pa, make the defect in substrate well be repaired.
Wherein, by the difference of substrate and target sense of rotation, it is possible to obtain the thin film of even compact.
According to one embodiment of the present invention, with BiFeO3As target, nickel acid lanthanum makes the silicon substrate of cushion as substrate, through pre-preparation, the step of the bismuth ferrite thin film of europium doping and repeat this two steps, obtains the Bi of different europium component1-xEuxFeO3Thin film, wherein x=0,0.03,0.05 or 0.07.
According to another embodiment of the present invention, in the preparation of the bismuth ferrite thin film of europium doping, by adjusting the sputtering target position in coating chamber, making focusing laser energy on different target position, open laser, sputtering obtains the Bi of different europium component1-xEuxFeO3Thin film, wherein x=0,0.03,0.05 or 0.07.Wherein, the Bi of different europium component is prepared by changing the target of sputtering1-xEuxFeO3Thin film.
In the present invention, the raw material preparing target includes europium oxide, bismuth oxide and ferrum oxide.The preparation process of target is, weighs the europium oxide of certain mass, bismuth oxide and ferrum oxide by counter balance, then three kinds of raw materials is utilized ball mill ball milling, makes three kinds of raw material mix homogeneously.Again the three of mix homogeneously kinds of raw material press being pressed into diameter is 5mm, thickness is the cylinder of 3mm, finally put it in Muffle furnace, heat up with the speed of per hour 5 DEG C, it is raised to 780 DEG C, air atmosphere sinters two hours, then is down to room temperature with the speed of per hour 5 DEG C, namely obtain required target.
In the present invention, the target that adopted europium doping is different obtains the Bi of different europium component1-xEuxFeO3Thin film, wherein x=0,0.03,0.05,0.07.Such as, with Bi0.97Eu0.03FeO3Bi is obtained as preparation of target materials0.97Eu0.03FeO3Thin film, with Bi0.95Eu0.05FeO3Bi is obtained as preparation of target materials0.95Eu0.05FeO3Thin film, with Bi0.93Eu0.07FeO3Bi is obtained as preparation of target materials0.93Eu0.07FeO3Thin film.
In the present invention, the method cleaning substrate is first remove oils and fats with liquid detergent, then removes liquid detergent residual with acetone, then puts into ultrasonic 30min in ethanol, takes out and be stored in alcoholic solution after being finally putting into deionized water for ultrasonic 30min.
Bi1 prepared by the inventive method-xEuxFeO3Thin film, along with the increase of Eu element in thin film, the crystal property of gained thin film, electric leakage performance are significantly improved, and optical band gap diminishes.Bismuth ferrite thin film (the Bi of rare-earth europium of the present invention doping1-xEuxFeO3Thin film), its photovoltaic performance be improved significantly, be suitable for the application in the devices field such as ferrum power production photovoltaic battery, CD-ROM driver, optical sensor.
Beneficial effect of the present invention includes, compared with prior art, and pulsed laser deposition simple in construction of the present invention and easy to operate.Meanwhile, target and substrate rotate simultaneously in different directions, it is possible to obtain uniform Bi1-xEuxFeO3Thin film；Can passing through underlayer temperature, sputtering pressure and backing material etc. control surface topography and the crystalline quality of thin film.
Additionally, utilize the pulsed laser deposition technique that the present invention adopts, by setting underlayer temperature, sputter oxygen pressure, it is possible to making the film composition prepared accurate, crystalline quality is good.The Bi that this method prepares is shown by XRD, AFM test1-xEuxFeO3Thin film has high crystalline quality, surfacing, moderate crystal grain size.
The preparation method course of reaction of the present invention is easily controllable, and raw material is easy to get.The Bi that the present invention prepares1-xEuxFeO3Thin film, along with the raising of europium doped elemental constituent, according to the ferroelectric hysteresis loop of detection it can be seen that electrical properties improves, band gap reduces, and is conducive to ferrum electricity Bi1-xEuxFeO3Thin film application in photovoltaic art.
Accompanying drawing explanation
Fig. 1 is the Bi prepared by the embodiment of the present invention 11-xEuxFeO3The X-ray diffraction figure (XRD) of (wherein x=0,0.03,0.05,0.07) thin film；
Fig. 2 is the BiFeO prepared by the embodiment of the present invention 13The atomic force microscope images (AFM) of thin film；
Fig. 3 is the Bi of the embodiment of the present invention 20.97Eu0.03FeO3The atomic force microscope images (AFM) of thin film；
Fig. 4 is the Bi of the embodiment of the present invention 30.95Eu0.05FeO3The atomic force microscope images (AFM) of thin film；
Fig. 5 is the Bi of the embodiment of the present invention 40.93Eu0.07FeO3The atomic force microscope images (AFM) of thin film；
Fig. 6 is the Bi of the embodiment of the present invention 1 to embodiment 4 preparation1-xEuxFeO3Ferroelectric hysteresis loop (P-E) image of (wherein x=0,0.03,0.05,0.07) thin film；
Fig. 7 is the Bi of the invention process embodiment 1 to embodiment 4 preparation1-xEuxFeO3The extinction coefficient image of (wherein x=0,0.03,0.05,0.07) thin film；
Fig. 8 is the Bi of the invention process embodiment 1 to embodiment 4 preparation1-xEuxFeO3The optical band gap image of (wherein x=0,0.03,0.05,0.07) thin film.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail, and the protected content of the present invention is not limited to following example.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage be all included in the present invention, and with appending claims for protection domain.Implementing the process of the present invention, condition, reagent, experimental technique etc., outside the lower content mentioned specially, be the universal knowledege of this area and known general knowledge, the present invention is not particularly limited content.
The preparation method of the bismuth ferrite thin film of the europium doping that the present invention proposes, comprises the steps:
(1) target: selecting purity is the Bi of 99.99%1-xEuxFeO3Target, 0≤x≤0.07.
(2) substrate: make the silicon substrate of cushion for substrate with nickel acid lanthanum, first remove oils and fats with liquid detergent, then remove liquid detergent residual with acetone, then put into ultrasonic 30min in ethanol, take out after being finally putting into deionized water for ultrasonic 30min and be stored in alcoholic solution.
(3) evacuation: be placed in coating chamber by target and substrate, utilizing mechanical pump and molecular pump that vacuum chamber is evacuated to pressure is 5 × 10-4Below pa.
(4) heating substrate:
Open firing equipment, control to make substrate be heated by the speed of intensification per minute 10 DEG C by computer.
(5) sputtering pressure is regulated:
Promoting temperature and arrive preset value 700 DEG C, open oxygen channel, regulate gas and pass into flow, then Molecular regulator pump slide valve makes sputtering pressure be 10Pa, is incubated 10min.Meanwhile, the distance regulating substrate and target is 6cm, and substrate base reverses, and target rotates forward.
(6) thin film deposition:
Unbalanced pulse laser instrument, makes single beam laser focus on Bi by lens with 45° angle1-xEuxFeO3On target, regulate laser energy and laser frequency.Preferably, adjustment laser energy is 200mJ, and the distance that adjustment laser frequency is 10Hz, target and substrate is adjusted to 6em, deposits 60min.
(7), after deposition terminates, it is incubated 30min.Then substrate is made to cool down with the speed of 20 DEG C per minute.It is cooled to less than 200 DEG C and takes out Bi1-xEuxFeO3(0≤x≤0.07) thin film, namely obtains purpose product.
Preparation method cost of material of the present invention is low, easy and simple to handle, and the film preparation cycle is short, is suitable for commercially producing requirement.Additionally, compared to other film preparing technologies, utilize pulsed laser deposition, by regulating the distance of the oxygen pressure in film deposition process, laser energy, target position and substrate, in that context it may be convenient to preparation component is accurate, the thin film that crystalline quality is good.
The present invention passes through rare-earth europium element doping, improves the crystal property of bismuth ferrite thin film, thus reducing leakage current, the electric property of bismuth ferrite thin film improves.Additionally, europium doping can also reduce the optical band gap of bismuth ferrite thin film, thus improving the bismuth ferrite absorption efficiency to sunlight, improve the photovoltaic performance of bismuth ferrite thin film.
Embodiment 1
(1) selection of target: adopting purity is the BiFeO of 99.99%3Target；
(2) clean nickel acid lanthanum and do the silicon substrate of cushion: this substrate can utilize sol-gal process to prepare on business silicon substrate.First with liquid detergent, remove oils and fats, then remove liquid detergent residual with acetone, then put into ultrasonic 30min in ethanol, take out after being finally putting into deionized water for ultrasonic 30min；
(3) evacuation: by BiFeO3Target and nickel acid lanthanum do the silicon substrate of cushion and are positioned in coating chamber, are fixed in substrate disc by substrate silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 × 10-4Below Pa；
(4) silicon: open firing equipment, uses computer control so that it is with 10 DEG C of intensifications per minute, be warmed up to 700 DEG C；
(5) temperature arrives preset value 700 DEG C, opens oxygen channel, pours the oxygen that purity is 99.99%, adjusting gas flow, then Molecular regulator pump slide valve, and obtaining sputtering pressure is 10Pa, and adjusting knob makes substrate base reverse simultaneously, and target rotates forward；
(6) unbalanced pulse laser instrument, laser focuses on BiFeO by lens with 45° angle3On target, arranging laser energy is 200mJ, and frequency is 10Hz, target and substrate distance is 6em, sedimentation time 60min；
(7), after insulation 30min, make substrate cool to less than 200 DEG C with speed 20 DEG C per minute, take out BiFeO3Thin film.
The Bi that the present embodiment prepares1-xEuxFeO3Thin film (wherein x=0), its XRD figure is as it is shown in figure 1, thin film shows obvious preferred orientation (h00), it was shown that Bi1-xEuxFeO3Thin film crystallization is of high quality.
As it is shown in figure 1, this Bi1-xEuxFeO3The crystallization direction of (wherein x=0) thin film is substantially (h00) crystal orientation.
It is illustrated in figure 2 BiFeO3The atomic force microscope figure of thin film, it was shown that the BiFeO that the inventive method prepares3Thin film crystal grain is relatively big, is about 125nm, and mean roughness is 5.2nm.
Embodiment 2
(1) selection of target: adopting purity is the Bi of 99.99%0.97Eu0.03FeO3Target；
(2) clean nickel acid lanthanum and do the silicon substrate of cushion: first with liquid detergent, remove oils and fats, then remove liquid detergent residual with acetone, then put into ultrasonic 30min in ethanol, take out after being finally putting into deionized water for ultrasonic 30min；
(3) evacuation: by Bi0.97Eu0.03FeO3Target and nickel acid lanthanum do the silicon substrate of cushion and are positioned in coating chamber, are fixed in substrate disc by substrate silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 × 10-4Below Pa；
(4) silicon: open firing equipment, uses computer control so that it is with 10 DEG C of intensifications per minute, be warmed up to 700 DEG C；
(5) temperature arrives preset value, opens oxygen channel, pours the oxygen that purity is 99.99%, adjusting gas flow, then Molecular regulator pump slide valve, and obtaining sputtering pressure is 10Pa, and adjusting knob makes substrate base reverse simultaneously, and target rotates forward；
(6) unbalanced pulse laser instrument, laser focuses on Bi by lens with 45° angle0.97Eu0.03FeO3On target, arranging laser energy is 200mJ, and frequency is 10Hz, target and substrate distance is 6cm, sedimentation time 60min；
(7), after insulation 30min, make substrate cool to less than 200 DEG C with speed 20 DEG C per minute, take out Bi0.97Eu0.03FeO3Thin film.
The Bi that the present embodiment prepares1-xEuxFeO3Thin film (wherein x=0.03), its XRD figure is as it is shown in figure 1, thin film shows obvious preferred orientation (h00), it was shown that Bi1-xEuxFeO3Thin film crystallization is of high quality.
As it is shown in figure 1, this Bi1-xEuxFeO3The crystallization direction of (wherein x=0.03) thin film is substantially (h00) crystal orientation.
It is illustrated in figure 3 Bi0.97Eu0.03FeO3The primary electron force microscope figure of thin film, it was shown that the Bi that the inventive method prepares0.97Eu0.03FeO3Thin film becomes fine and close, and mean roughness is 4.1nm.
Embodiment 3
(1) selection of target: adopting purity is the Bi of 99.99%0.95Eu0.05FeO3Target；
(2) clean nickel acid lanthanum and do the silicon substrate of cushion: first with liquid detergent, remove oils and fats, then remove liquid detergent residual with acetone, then put into ultrasonic 30min in ethanol, take out after being finally putting into deionized water for ultrasonic 30min；
(3) evacuation: by Bi0.95Eu0.05FeO3Target and nickel acid lanthanum do the silicon substrate of cushion and are positioned in coating chamber, are fixed in substrate disc by substrate silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 × 10-4Below Pa；
(4) silicon: open firing equipment, uses computer control so that it is with 10 DEG C of intensifications per minute, be warmed up to 700 DEG C；
(5) temperature arrives preset value, opens oxygen channel, pours the oxygen that purity is 99.99%, adjusting gas flow, then Molecular regulator pump slide valve, and obtaining sputtering pressure is 10Pa, and adjusting knob makes substrate base reverse simultaneously, and target rotates forward；
(6) unbalanced pulse laser instrument, laser focuses on Bi by lens with 45° angle0.95Eu0.05FeO3On target, arranging laser energy is 200mJ, and frequency is 10Hz, target and substrate distance is 6cm, sedimentation time 60min；
(7), after insulation 30min, make substrate cool to less than 200 DEG C with speed 20 DEG C per minute and take out Bi0.95Eu0.05FeO3Thin film.
The Bi that the present embodiment prepares1-xEuxFeO3Thin film (wherein x=0.05), its XRD figure is as it is shown in figure 1, thin film shows obvious preferred orientation (h00), it was shown that Bi1-xEuxFeO3Thin film crystallization is of high quality.
As it is shown in figure 1, this Bi1-xEuxFeO3The crystallization direction of (wherein x=0.05) thin film is substantially (h00) crystal orientation.
It is illustrated in figure 4 Bi0.95Eu0.05FeO3The primary electron force microscope figure of thin film, it was shown that the Bi that the inventive method prepares0.95Eu0.05FeO3Thin film crystal grain diminishes, and is about 100nm, and mean roughness is 3.6nm.
Embodiment 4
(1) selection of target: adopting purity is the Bi of 99.99%0.93Eu0.07FeO3Target；
(2) clean nickel acid lanthanum and do the silicon substrate of cushion: first with liquid detergent, remove oils and fats, then remove liquid detergent residual with acetone, then put into ultrasonic 30min in ethanol, take out after being finally putting into deionized water for ultrasonic 30min；
(3) evacuation: by Bi0.93Eu0.07FeO3Target and nickel acid lanthanum do the silicon substrate of cushion and are positioned in coating chamber, are fixed in substrate disc by substrate silver slurry, and utilizing mechanical pump and molecular pump that vacuum is evacuated to pressure is 5 × 10-4Below Pa；
(4) silicon: open firing equipment, uses computer control so that it is with 10 DEG C of intensifications per minute, be warmed up to 700 DEG C；
(5) temperature arrives preset value, opens oxygen channel, pours the oxygen that purity is 99.99%, adjusting gas flow, then Molecular regulator pump slide valve, and obtaining sputtering pressure is 10Pa, and adjusting knob makes substrate base reverse simultaneously, and target rotates forward；
(6) unbalanced pulse laser instrument, laser focuses on Bi by lens with 45° angle0.93Eu0.07FeO3On target, arranging laser energy is 200mJ, and frequency is 10Hz, target and substrate distance is 6cm, sedimentation time 60min；
(7), after insulation 30min, make substrate cool to less than 200 DEG C with speed 20 DEG C per minute and take out BI0.93Eu0.07FeO3Thin film.
The Bi that the present embodiment prepares1-xEuxFeO3Thin film (wherein x=0.07), its XRD figure is as it is shown in figure 1, thin film shows obvious preferred orientation (h00), it was shown that Bi1-xEuxFeO3Thin film crystallization is of high quality.
As it is shown in figure 1, this Bi1-xEuxFeO3The crystallization direction of (wherein x=0.07) thin film is substantially (h00) crystal orientation.
It is illustrated in figure 5 Bi0.93Eu0.07FeO3The primary electron force microscope figure of thin film, it was shown that the Bi that the inventive method prepares0.93Eu0.07FeO3Thin film is finer and close, and surface is more smooth, and mean roughness is reduced to 2.0nm.
To the Bi prepared by above example 1-41-xEuxFeO3Leakage property that thin film (wherein x=0,0.03,0.05,0.07) carries out, band gap etc. detect, and result is as shown in figs 6-8.
Bi as shown in Figure 61-xEuxFeO3The ferroelectric hysteresis loop of thin film (wherein x=0,0.03,0.05,0.07) is visible, and along with the increase of europium doped element, remanent polarization becomes big, and the leakage current of thin film reduces.
It is illustrated in figure 7 the Bi that elliptically polarized light matching obtains1-xEuxFeO3The extinction coefficient image of thin film (wherein x=0,0.03,0.05,0.07) is visible, along with the increase of europium doped element, the maximum generation red shift of extinction coefficient k.
It is illustrated in figure 8 and utilizes the calculated Bi of extinction coefficient1-xEuxFeO3The optical band gap image of thin film (wherein x=0,0.03,0.05,0.07) is visible, and along with the increase of europium doped element, the band gap of thin film reduces.
Visible according to above experimental result, the present invention improves the photovoltaic performance of bismuth ferrite thin film by introducing rare-earth europium element doping.Along with the increase of Eu element in thin film, the crystal property of gained thin film, electric leakage performance substantially improves, and optical band gap diminishes.Along with the increase of rare-earth europium element doping amount, Bi1-xEuxFeO3The mean roughness of thin film is reduced to 2nm from 5.2nm, illustrates that the doping of rare-earth europium improves Bi1-xEuxFeO3The crystalline quality of thin film；Along with the increase of rare-earth europium element doping amount, Bi1-xEuxFeO3The remanent polarization of thin film is from 2.5uC/cm-2Increase to 7.5uC/cm-2, Bi is described1-xEuxFeO3The electric property of thin film improves；Along with the increase of rare-earth europium element doping amount, Bi1-xEuxFeO3The optical band gap of thin film is reduced to 2.6eV from 2.78eV, and europium element doping can improve Bi1-xEuxFeO3The thin film absorption efficiency to sunlight, thus improving Bi1-xEuxFeO3The photovoltaic performance of thin film.
As can be seen here, the Bi that the present invention is prepared by europium doped element1-xEuxFeO3Thin film (wherein x=0,0.03,0.05 or 0.07) achieves and significantly improves BiFeO3The photovoltaic performance of thin film.
Claims (2)
1. the bismuth ferrite thin film of an europium doping, it is characterised in that including substrate and target, described target material deposition is over the substrate；
Wherein, the silicon substrate that described substrate is is cushion with nickel acid lanthanum, described target composition formula is Bi1-xEuxFeO3, x=0.03,0.05 or 0.07；
Wherein, the preparation method of the bismuth ferrite thin film of described europium doping comprises the steps:
A) pre-preparation
The Bi being 99.99% with purity1-xEuxFeO3As target, wherein x=0.03,0.05 or 0.07；The silicon substrate of cushion is made as substrate using nickel acid lanthanum；
Described substrate is cleaned, described target and described substrate are positioned in coating chamber, regulate coating chamber pressure to 5 × 10-4Below Pa；
B) preparation of the bismuth ferrite thin film of europium doping
To described silicon；Described substrate is made to be warming up to 700 DEG C with the speed of 10 DEG C per minute；Being filled with the oxygen that purity is 99.99%, adjusting gas flow makes sputtering pressure be 10Pa；Temperature 700 DEG C, keep 10 minutes when oxygen pressure 10Pa；
Described substrate reverses, and described target rotates forward；The distance regulating described substrate and described target is 6cm；
Arranging pulse laser, making laser energy is 200mJ, and laser frequency is 10Hz；
Opening described pulse laser and carry out thin film deposition, sedimentation time is 60min；Then 30min it is incubated；
Lower the temperature with the speed of 20 DEG C per minute, take out the film sample that deposition obtains during to 200 DEG C, obtain the bismuth ferrite thin film of described europium doping；
Repeat the preparation process of the bismuth ferrite thin film of described pre-preparation, europium doping, and by adjusting the sputtering target position in coating chamber, make focusing laser energy on different target position, thus sputtering obtains the Bi of different europium component1-xEuxFeO3Thin film, wherein x=0.03,0.05 or 0.07；
The method that described substrate cleans is: cleans described substrate with liquid detergent, acetone successively, then takes out after ethanol, deionized water for ultrasonic 30min successively, is stored in alcoholic solution.
2. the bismuth ferrite thin film of europium doping as described in the appended claim 1 application in ferrum power production photovoltaic battery, CD-ROM driver, optical sensor.
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| CN104388894B (en) * | 2014-12-09 | 2018-09-21 | 湖北大学 | The method that pulsed laser deposition prepares low band gaps ferroelectricity photovoltaic film |
| CN111074244A (en) * | 2018-10-19 | 2020-04-28 | 营口理工学院 | Nickel-cerium co-doped bismuth ferrite film material and preparation method thereof |
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